JP3927685B2 - Novel hydrocarbon alcohol, hydrocarbon epoxy resin and process for producing the same - Google Patents

Description

【００１８】
【化１８】

【００１９】
【化１９】

【００２０】
本発明の炭化水素アルコールは、炭化水素・フェノール樹脂を核水素化反応することにより製造する。
原料の炭化水素・フェノール樹脂は以下の方法で製造できる。
すなわち、酸触媒の存在下にて、フェノール性水酸基を１〜３個有する炭素数６〜１６のフェノール類と炭素−炭素二重結合を２個以上有する炭素数４〜２５の不飽和炭化水素を反応させることで製造する。
【００２１】
該不飽和炭化水素としては、イソプレン、ブタジエン、ピペリレン、ヘキサジエン、オクタトリエンなどの炭素数４〜２５の非環状ポリエン類、シクロペンタジエン、メチルシクロペンタジエン、シクロヘキサジエン、シクロオクタジエン、リモネン、ピネン、ビニルシクロヘキセン、ビニルノルボルネン、テトラヒドロインデン、ジシクロペンタジエン、メチルジシクロペンタジエンなどの炭素数５〜２５の脂環式不飽和炭化水素、ジビニルベンゼンなどの芳香族ジエン類およびこれらの不飽和炭化水素のディールス・アルダー反応生成物を挙げることができる。使用に際しては単独若しくは混合物として用いることができる。
【００２２】
これらの化合物の多くは、いずれもＥＰＤＭ（エチレン・プロピレン・ジエン・メチレンゴム）の第三成分である５−エチリデンノルボルネンの製造プラントにおける原料、中間原料または副生物で、工業的に安価に入手することができる。
【００２３】
炭化水素・フェノール樹脂として、結節基として環状炭化水素基を希望する場合は、通常、原料の不飽和炭化水素は通常、環状の炭化水素を用いるが、オクタトリエンなどの非環状の不飽和炭化水素を用いてもアルキル化反応とともに環化反応が起こり所望の環状炭化水素・フェノール樹脂を製造することができる。
【００２４】
該フェノール類としては、例えばフェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｏ−エチルフェノール、ｍ−エチルフェノール、ｐ−エチルフェノール、ｏ−イソプロピルフェノール、ｍ−プロピルフェノール、ｐ−プロピルフェノール、ｐ−ｓｅｃ−ブチルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−シクロヘキシルフェノール、ｐ−クロロフェノール、ｏ−ブロモフェノール、ｍ−ブロモフェノール、ｐ−ブロモフェノール、α−ナフトール、β−ナフトール等の一価フェノール類；レゾルシン、カテコール、ハイドロキノン、２，２−ビス（４’−ヒドロキシフェニル）プロパン、１，１’−ビス（ジヒドロキシフェニル）メタン、１，１’−ビス（ジヒドロキシナフチル）メタン、テトラメチルビフェノール、ビフェノール等の二価フェノール類；トリスヒドロキシフェニルメタン等の三価フェノール類及びこれらの混合物等を好ましく挙げることができる。特にフェノール、ｏ−クレゾール、ｍ−クレゾール、α−ナフトール、β−ナフトール及び２，２−ビス（４’−ヒドロキシフェニル）プロパン等は経済性及び製造の容易さの点から望ましい。
【００２５】
該フェノール類と該炭化水素との仕込み割合は、該フェノール類を該炭化水素に対して通常０．８〜１２倍モル当量、好ましくは１〜８倍モル当量用いることが望ましい。該フェノール類の仕込み割合が０．８倍モル当量未満の場合には、該炭化水素の単独重合が併発し、１２倍モル当量を超える場合には、未反応のフェノール類の回収が困難となるので好ましくない。
【００２６】
該フェノール類と該炭化水素とを反応させる際に用いる酸触媒としては、三フッ化ホウ素；三フッ化ホウ素のエーテル錯体、水錯体、アミン錯体、フェノール錯体またはアルコール錯体等の三フッ化ホウ素錯体；三塩化アルミニウム、ジエチルアルミニウムモノクロリド等のアルミニウム化合物；塩化鉄；四塩化チタン；硫酸；フッ化水素；トリフルオロメタンスルホン酸等を好ましく使用することができ、特に活性と触媒の除去の容易さの点から三フッ化ホウ素、三フッ化ホウ素錯体が好ましく、さらには三フッ化ホウ素、三フッ化ホウ素・フェノール錯体が最も好ましい。
【００２７】
該酸触媒の使用量は特に限定されるものではなく、使用する触媒により適宜選択することができるが、例えば三フッ化ホウ素・フェノール錯体の場合は、炭化水素１００重量部に対して０．１〜２０重量部、好ましくは０．５〜１０重量部とするのが好ましい。
【００２８】
該フェノール類と該炭化水素との反応は、溶剤を使用しても使用しなくても実施することができ、溶剤を使用しない場合は該フェノール類を該炭化水素に対して等モル当量以上用いるのが好ましく、特に３〜１２倍モル当量用いるのが好ましい。溶剤を使用する場合、該溶剤としては、反応を阻害しない溶剤であれば特に制限されないが、特に好ましい溶剤としてはベンゼン、トルエン、キシレン等の芳香族炭化水素化合物等が挙げられる。
【００２９】
前記反応の反応温度は、使用する酸触媒の種類により異なるが、例えば三フッ化ホウ素・フェノール錯体を使用した場合は、通常２０〜１７０℃、好ましくは５０〜１５０℃である。反応温度が１７０℃を超える場合には、触媒の分解又は副反応が生じ、また２０℃未満の場合には、反応に長時間を要し、経済的に不利であるので好ましくない。
【００３０】
また前記反応において、反応を円滑に進行させるためには、系内の水分をできるだけ少なくするのが好ましく、特に１００重量ｐｐｍ以下に保つことが好ましい。更に前記反応においては、前記炭化水素を逐次的に添加しながら重合を行うのが、前記炭化水素の単独重合の防止、並びに反応熱制御の点で好ましい。
【００３１】
本製造方法においては、前記反応終了後、触媒の失活を行う。
失活の手段は特に制限されないが、最終的に得られる樹脂中のホウ素、フッ素等のイオン性不純物の残存量が１００ｐｐｍ以下となるような手段を用いるのが合成上好ましい。
この目的のために用いる試薬としては、アルカリ金属、アルカリ土類金属もしくはそれらの酸化物、水酸化物、炭酸塩、水酸化アンモン、アンモニアガス等無機塩基類等を用いることもできるが、処理が簡潔で速く、かつ処理後のイオン性不純物の残存量も少ないハイドロタルサイト類を用いるのが好ましい。
本製法においては、ハイドロタルサイト類等で酸触媒を失活および吸着した後、酸触媒を吸着したハイドロタルサイト類等をろ過除去して、触媒残差を全く含まない反応液を回収し、次いで反応液を蒸留濃縮することにより高純度の炭化水素・フェノール樹脂を得ることができる。
【００３２】
次に、本発明の炭化水素アルコールの製造方法について詳細に説明する。
前述の炭化水素・フェノール樹脂を溶媒に希釈し、金属触媒を用いて接触水素化することにより炭化水素アルコールを製造することができる。
まず前述のフェノール樹脂類を溶媒に希釈する。希釈に用いる溶媒は特に限定されるものではないが、メタノール、エタノール、イソプロパノール、イソブタノール等の低級アルコールが適しており、中でもイソプロパノール、イソブタノールを用いた場合、活性が高く好ましい。
溶媒の使用量にも特に限定はないが、通常原料の該フェノール樹脂に対して１〜２重量倍の範囲で選択される。
水素化反応は、希釈溶液中で金属触媒と炭化水素・フェノール樹脂を接触させて行う。
【００３３】
用いる金属触媒は特に制限されるものではなく、反応時間や条件に応じて適宜選択でき、例えば、ニッケル系触媒、パラジウム系触媒、ルテニウム系触媒、ロジウム系触媒などを好ましく挙げることができる。中でも比較的安価で入手しやすく、反応活性の高いラネーニッケル系触媒を用いるのが特に好ましい。また、ラネーニッケルは単独で用いてもよいが、活性を高めるためにアルカリ土類金属水酸化物等の共触媒化合物を適宜添加してもよい。
【００３４】
本発明におけるラネーニッケルの使用量は原料のフェノール樹脂に対して０．５〜１０重量％、好ましくは１〜５重量％の範囲で用いるのが良いが、これに限定されるものではなく、反応時間をより短縮しようとする場合には、これよりも多量のラネーニッケルを用いることもできる。
反応条件は活性に応じて変更が可能だが、反応温度としては、８０〜２２０℃、好ましくは１００℃〜２００℃の範囲が採用され、水素圧は２〜３ｋｇ／ｃｍ² 以上であれば、どのような圧でも構わないが、好ましくは５〜１５０ｋｇ／ｃｍ² 、より好ましくは４０〜６０ｋｇ／ｃｍ² の範囲で行う。
反応は高圧用オートクレーブ中で、適宜希釈した原料フェノール樹脂に、所定量のラネーニッケル触媒あるいはパラジウム触媒と必要に応じてアルカリ土類金属水酸化物を供給し、オートクレーブ内を水素で置換後加熱撹拌して行う。反応の進行にしたがって水素圧が低下するので、補給を繰り返しつつ水素圧が下がらなくなることを確認した後、加熱撹拌を止めてオートクレーブを冷却する。
反応終了後、反応混合物をろ過して、触媒および触媒残残さのまったくない反応液を回収し、溶媒を蒸留濃縮して留去することにより、蒸留残の形で目的とする新規な炭化水素アルコールを得る。
【００３５】
濃縮は常圧、減圧、加圧下もしくはこれらの併用のいずれで行っても良い。濃縮温度は８０℃〜３００℃の範囲で行うのが好ましく、より好ましくは１０℃〜２７０℃、さらに好ましくは１３０℃〜２５０℃の範囲で行うのが良い。濃縮温度が３００℃を超えると樹脂の分解、脱水反応等を併発する恐れがあるのでこの温度以下で行うのが好ましい。また、濃縮を円滑にかつ迅速にすませるため、濃縮系内に窒素もしくは水蒸気を吹き込んでも良い。
【００３６】
本発明の炭化水素アルコールは、ポリエステル樹脂の原料として使用することができるが、後述のようにエポキシ樹脂原料として最適である。また、本発明の炭化水素アルコールにα、β−酸無水物で半エステル化しカルボン酸基を導入した樹脂は、短波長領域に吸収がないため、半導体レジスト原料として好ましく使用できる。特に結節基が飽和多環炭化水素骨格である炭化水素アルコールまたはこのｔ−ブチルエステル類は、１９０〜３００ｎｍで光吸収が無く、しかもドライエッチング耐性が高いため、半導体用レジスト特にＡｒＦエキシマレーザー用レジスト原料として最適である。
【００３７】
本発明の炭化水素エポキシ樹脂は、該炭化水素アルコールをグリシジル化することにより得ることができ、該グリシジル化反応は脂環式アルコールの場合と同様な方法を採用することができる。具体的には、例えば、水酸化ナトリウム、水酸化カリウム等の塩基の存在下、通常１０〜１５０℃、好ましくは３０〜８０℃の温度で、該炭化水素アルコールを、エピクロルヒドリン、エピブロムヒドリン等のグリシジル化剤と反応させたのち、水洗、乾燥することにより得ることができる。この際グリシジル化剤の使用量は、炭化水素アルコールに対して好ましくは２〜２０倍モル当量、特に好ましくは３〜７倍モル当量である。
また反応の際、減圧下にて、グリシジル化剤との共沸蒸留により水を留去することによって反応をより速く進行させることができる。また本発明の炭化水素エポキシ樹脂を電子分野で使用する場合、前記エポキシ樹脂において、副生する塩化ナトリウムは、水洗工程で完全に除去しておかなければならない。この際グリシジル化剤を蒸留により回収して反応溶液を濃縮した後、該濃縮物を溶剤に溶解し、水洗してもよい。該溶剤としては、メチルイソブチルケトン、シクロヘキサノン、ベンゼン、ブチルセロソルブ等を好ましく挙げることができる。該水洗した濃縮物は、水洗後、加熱濃縮することにより、炭化水素エポキシ樹脂とすることができる。
【００３８】
前記エポキシ樹脂中のエポキシ基の含量は、通常２００〜５００ｇ／グラム当量、好ましくは２５０〜４５０ｇ／グラム当量であるのが望ましい。エポキシ基の含量が５００ｇ／グラム当量未満の場合には、架橋密度が低くなりすぎるため好ましくない。
【００３９】
本発明の炭化水素エポキシ樹脂を用いてエポキシ樹脂組成物として使用する場合の条件について、以下に詳細に説明する。
本発明のエポキシ樹脂組成物は、（ａ）前記エポキシ樹脂を含めた硬化性エポキシ樹脂（以下（ａ）成分と称す）、（ｂ）フェノール樹脂（以下（ｂ）成分と称す）、（ｃ）硬化促進剤（以下（ｃ）成分と称す）を必須成分として含有することを特徴とする。
【００４０】
本発明のエポキシ樹脂組成物において（ａ）成分として用いる硬化性エポキシ樹脂は前記の新規炭化水素エポキシに加えて、さらに分子中にエポキシ基を少なくとも１個、好ましくは２個以上有する樹脂であって、例えばエピクロルヒドリンとビスフェノールＡやノボラック樹脂から合成されるエポキシ樹脂、ジシクロペンタジエン、ビニルシクロヘキセン等のモノまたはジエポキシド等の脂環式エポキシ樹脂、テトラメチルビスフェノールジグリシジルエーテル、トリグリシジルイソシアヌレート、テトラグリシジルジアミノジフェニルメタン等の特殊エポキシ樹脂及びこれらのエポキシ樹脂に塩素原子や臭素原子等のハロゲン原子を導入したエポキシ樹脂等を挙げることができ、使用に際しては単独もしくはこれらのエポキシ樹脂の２種以上の混合物として用いることができる。
また前記（ａ）成分としては、市販品を用いることもでき、例えばノボラックエポキシ樹脂としては、商品名「エピクロンＮ−６６０」（大日本インキ化学工業（株）製）、「スミエポキシＥＳＣＮ−１９５Ｘ」（住友化学工業（株）製）、「ＱＵＡＴＲＥＸ２４１０」（ダウケミカル（株）製）、「ＥＯＣＮ−１００」（日本化薬（株）製）、「ＹＤＣＮ−７０２Ｐ」（東都化成（株）製）、特殊エポキシ樹脂としては、「ＹＸ−４０００」（油化シェルエポキシ（株）製）、「ＥＰＩＣＬＯＮ ＥＸＡ−１５１４」、「ＥＰＩＣＬＯＮＨＰ−４０３２」、「ＥＰＩＣＬＯＮ ＥＸＡ−１８５７」（大日本インキ化学工業（株）製）、「エピコート１５７Ｓ６５」、「エピコートＹＬ９３３」（油化シェルエポキシ（株）製）、「ＶＧ−３１０１」（三井石油化学（株）製）等が挙げられる。
【００４１】
本発明のエポキシ樹脂組成物において（ｂ）成分として用いるフェノール樹脂は特に限定されるものではないが、好ましくは前記一般式化１で示される分子量２６８〜２０００のフェノール樹脂等を挙げることができる。また前記フェノール樹脂は、フェノール樹脂を単離していない、未反応物やフェノール樹脂以外の反応物を含むものをそのまま使用することもできる。
【００４２】
本発明のエポキシ樹脂組成物に使用する（ｃ）成分の硬化促進剤としては、エポキシ基とフェノール性水酸基との反応を促進するものであればよく、一般に半導体封止用に使用される、例えば第三級ホスフィン類、イミダゾール類、第三級アミン類等を用いることができる。具体的には、前記第三級ホスフィン類としては、例えばトリエチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン等を好ましく挙げることができる。また前記第三級アミンとしては、例えばジメチルエタノールアミン、ジメチルベンジルアミン、２，４，６−トリス（ジメチルアミノ）フェノール、１，８−ジアザビシクロ［５．４．０］ウンデセン等を好ましく挙げることができる。前記イミダゾール類としては、例えば２−エチル−４−メチルイミダゾール、２，４−ジメチルイミダゾール、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、１−ビニル−２−メチルイミダゾール、１−プロピル−２−メチルイミダゾール、２−イソプロピルイミダゾール、１−シアノエチル−２−エチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、２−フェニルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−フェニル−４−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール等を挙げることができる。前記（ｃ）成分として、特に好ましくは２−メチルイミダゾール、ジアザビシクロウンデセン（ＤＢＵ）、トリフェニルホスフィン、ジメチルベンジルアミン又はこれらの混合物等を挙げることができる。
【００４３】
本発明のエポキシ樹脂組成物に使用する（ａ）〜（ｃ）各成分の配合割合は、（ａ）成分１００重量部に対し、（ｂ）成分が好ましくは２０〜１８０重量部、さらに好ましくは３０〜１２０重量部、（ｃ）成分が好ましくは０．０１〜７．０重量部、さらに好ましくは０．５〜５．０重量部である。
本発明の半導体封止用エポキシ樹脂組成物は、前記（ａ）〜（ｃ）成分に加えて、さらに（ｄ）無機充填材（以下（ｄ）成分と称す）を必須成分として含有することを特徴とする。
本発明の半導体封止用エポキシ樹脂組成物において、必須成分として用いる（ａ）、（ｂ）および（ｃ）成分としては、前記エポキシ樹脂組成物に挙げた樹脂および化合物等をいずれも好ましく使用することができる。また（ｄ）成分として用いる無機充填材としては、一般にシリカ粉末充填剤等を好ましく用いることができる。尚、このシリカ粉末充填剤は溶融させて用いても良い。
【００４４】
本発明の半導体封止用エポキシ樹脂組成物に使用する（ａ）〜（ｄ）各成分の配合割合は、（ａ）成分１００重量部に対し、（ｂ）成分が好ましくは２０〜１８０重量部、さらに好ましくは３０〜１２０重量部、（ｃ）成分が好ましくは０．０１〜７．０重量部、さらに好ましくは０．５〜５．０重量部であり、更に（ｄ）成分の配合割合は、半導体封止用エポキシ樹脂組成物全体に対して、好ましくは５０〜９０重量％、さらに好ましくは６５〜８５重量％の範囲である。
【００４５】
本発明の半導体封止用エポキシ樹脂組成物は、前記（ａ）〜（ｄ）の各成分を必須成分として含有するが、必要に応じて前記（ｂ）成分以外のフェノール樹脂等を含有させることもできる。前記（ｂ）成分以外のフェノール樹脂としては、例えば商品名「タマノール−７５８」、「タマノール−７５９」（荒川化学工業（株）製）、「ＥＣＮ−１２８０」（チバガイギー（株）社製）等のノボラック型フェノール樹脂、臭素化ノボラック型フェノール樹脂、ポリビニルフェノール、臭素化ポリビニルフェノール、テトラブロモビスフェノールＡ等の多価フェノール化合物等を挙げることができる。前記（ｂ）成分以外のフェノール樹脂の使用量は、前記（ｂ）成分１００重量部に対し１００重量部以下、特に５０重量部以下とするのが好ましい。前記使用量が１００重量部を超えると耐湿性が悪くなるので好ましくない。
【００４６】
本発明の半導体封止用エポキシ樹脂組成物には、シランカップリング剤、ブロム化エポキシ樹脂、三酸化アンチモン、ヘキサブロモベンゼン等の難燃剤、カーボンブラック、ベンガラ等の着色剤、天然ワックス、合成ワックス等の離型剤、シリコンオイル、ゴム等の低応力添加剤等の種々の添加剤を適宜配合することもできる。
【００４７】
本発明の半導体封止用エポキシ樹脂組成物を用いて成型材料を調製するには、必須成分と、また必要に応じてその他の添加剤とをミキサー等によって十分に均一に混合した後、更に熱ロールまたはニーダー等で溶融混練し、射出あるいは冷却後粉砕するなどして得ることができる。
【００４８】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
［合成例１］
炭化水素・フェノール樹脂（Ｐ−１）の合成
フェノール２０００ｇとトルエン４００ｇとを、還流冷却器及びリービッヒコンデンサーを備えた容量５リットルの反応器に仕込み、１７０℃に加熱して、トルエン３５０ｇを留出し、反応系内の水分含有量を７０ｐｐｍとした。次いで、反応系を７０℃まで冷却し、三フッ化ホウ素・フェノール錯体１０ｇを添加した後、反応温度を７０℃に制御しながら、水分含有量が２０ｐｐｍのジシクロペンタジエン４００ｇを１．５時間かけて徐々に滴下し、滴下終了後、１００℃で５時間反応を行った。反応終了後、得られた反応物にＭｇ_0.7 Ａｌ_0.3 （ＯＨ）₂ （ＣＯ₃ ）_0.15・ｍＨ₂ Ｏ（但し、０．４６≦ｍ≦０．５４）で表されるハイドロタルサイト化合物（協和化学工業社製合成ハイドロタルサイト・商品名「ＫＷ−１０００」）３０ｇ添加し、３０分間攪拌して触媒を失活させた後、セライトを敷き詰めたろ紙を用いて反応液をろ過した。得られた反応液を２１０℃で減圧蒸留を行い８８０ｇのフェノール樹脂を得た。この樹脂中のフェノール残量を測定したところ１０ｐｐｍであった。
【００４９】
得られたフェノール樹脂（Ｐ−１）は軟化点が９６℃、ガードナー色相１３、残存ホウ素５ｐｐｍ、フッ素は１ｐｐｍ以下であった。
炭水素分析法による炭素、水素の含有量はそれぞれ、８３．０％、７．６％、酸素定量法による酸素の含有量は９．５％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量３２０、５４６、７７１、９９７、１２２３のピークが検出され、式（１０）に示した構造の分子で構成されていることが確認された。
フェノール性水酸基の含有量を、無水酢酸でアセチル化した後、逆滴定により求めたところ、フェノール性水酸基当量は１７０ｇ／ｅｑであった。
【００５０】
¹Ｈ−ＮＭＲ分析では、δ ６．５〜７．５ｐｐｍに芳香環に結合したプロトンが、またδ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンがそれぞれ多重線で観測され、炭素−炭素二重結合に起因するプロトンの吸収は認められなかった。またδ ６．５〜８ｐｐｍとδ ０．８〜２．５ｐｐｍとのピーク面積比よりフェノール性水酸基の含有量を求めたところ、滴定による結果と同様にフェノール性水酸基当量は１７０ｇ／ｅｑであった。
【００５１】
また、¹³Ｃ−ＮＭＲ分析では、フェノールが二重結合にエーテル付加した場合に生じる１５８ｐｐｍの炭素のシグナルが観測されないことからフェノールはいずれもアルキレーションで付加していることがわかった。
【００５２】
【化２０】

【００５３】
炭化水素アルコール（Ａ−１）の水素化
上記の炭化水素・フェノール樹脂（Ｐ−１）の水素化を以下の方法で行った。
撹拌器を取り付けたＳＵＳ３０４製の１ｌオートクレーブに、実施例１で得られたフェノール樹脂（Ｐ−１）１７０ｇ、イソプロパノール３４０ｇ、ラネーニッケル１０．０ｇを仕込み、オートクレーブ内を水素で置換した後、１８０℃に昇温した。
続いて、反応系内温度を１８０℃に維持しながら、水素圧を６０ｋｇ／ｃｍ² に昇圧し、４０ｋｇ／ｃｍ² まで下がったら再度昇圧する工程を水素吸収が無くなるまで継続したところ、８時間後に吸収が終了した。
オートクレーブを冷却し、反応液をろ過して、触媒および触媒残さを除去した後、残留反応液を蒸留、濃縮したところ１６７ｇを得た。
【００５４】
淡水素分析法による炭素、水素の含有量はそれぞれ８０．２％、１０．８％、酸素定量法による酸素の含有量は９．３％であった。
得られた樹脂のＦＤマススペクトルを測定したところ分子量３３２、５６４、７９５、１０２７、１２５９のピークが検出された。
得られた誘導体の、水酸基当量を測定したところ１７９ｇ／ｅｑであった。
また、 ¹Ｈ−ＮＭＲ分析では、δ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンが多重線で観測されたが、炭素−炭素二重結合に起因するプロトンの吸収は認められず、δ ６．５〜７．５ｐｐｍの芳香環に結合したプロトンが消失しており、水素化が完了したことが確認された。
ＩＲによる分析においてもＰ−１では３０５０ｃｍ^-1付近に見られた芳香族のＣ−Ｈ伸縮に由来するピークが消失しており、得られた樹脂が目的とする淡黄色の式（１１）に示した炭化水素アルコール誘導体（Ａ−１）であることを確認した。
【００５５】
【化２１】

【００５６】
炭化水素エポキシ樹脂（Ｅ−１）の合成
上記の炭化水素アルコール（Ａ−１）のグリシジル化を以下の方法で行った。
攪拌機、還流冷却器および温度計付きの２リットル４つ口フラスコに炭化水素アルコール（Ａ−１）１７９ｇとエピクロルヒドリン７００ｇとを仕込んだ後、溶解、攪拌し、反応系内を１５０ｍｍＨｇの圧力に調製し、６８℃に昇温した。この系に濃度４８重量％の水酸化ナトリウム水溶液１００ｇを連続的に添加しながら３．５時間反応させた。該反応により生成する水および水酸化ナトリウム水溶液の水を、水−エピクロルヒドリン共沸混合物の還流により分解し、反応系外へ連続的に除去した。反応終了後、反応系を常圧に戻し１１０℃の温度まで昇温して反応系の水を完全に除去した。過剰のエピクロルヒドリンを常圧下で蒸留除去し、さらに１５ｍｍＨｇの減圧下に１４０℃で蒸留を行なった。
【００５７】
生成した樹脂および塩化ナトリウムの混合物に、メチルイソブチルケトン３００ｇおよび１０重量％の水酸化ナトリウム水溶液３６ｇを加え、８５℃の温度で１．５時間反応を行なった。反応終了後、メチルイソブチルケトン７５０ｇおよび水３００ｇを加え、下層の塩化ナトリウム水溶液を分液除去した。次にメチルイソブチルケトン液層に水１５０ｇを加えて洗浄し、リン酸で中和し、水層を分離したのちさらに水８００ｇで洗浄し水層を分離した。
次いで、メチルイソブチルケトン液層を常圧下で蒸留したのち、５ｍｍＨｇ、１４０℃で減圧蒸留を行い、下記式（１２）で表される２２０ｇの炭化水素エポキシ樹脂（Ｅ−１）を得た。このエポキシ樹脂のエポキシ当量は２５０ｇ／当量であった。
【００５８】
【化２２】

【００５９】
［合成例２］
フェノール樹脂（Ｐ−２）の合成
フェノールの代わりにｏ−クレゾールを２３００ｇ用いた以外は、実施例１と同様に反応、精製を行い、下記式（１３）で表わされるフェノール樹脂（Ｐ−２）９４０ｇを得た。
【００６０】
【化２３】

【００６１】
得られたフェノール樹脂（Ｐ−２）は、軟化点が８９℃、ガードナー色相は１１、残存ホウ素は５ｐｐｍ、フッ素は１ｐｐｍ以下であった。
炭水素分析法による炭素、水素の含有量はそれぞれ、８３．０％、８．１％、酸素定量法による酸素の含有量は９．１％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量３４８、５８８、８２８、１０６８、１３０８のピークが検出され、式（１３）に示した構造の分子で構成されていることが確認された。フェノール性水酸基当量は１８０ｇ／ｅｑであった。
¹Ｈ−ＮＭＲ分析では、δ ６．５〜７．５ｐｐｍに芳香環に結合したプロトンが、またδ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンが多重線で観測され、炭素−炭素二重結合に起因するプロトンの吸収は認められなかった。またδ ６．５〜８ｐｐｍとδ ０．８〜２．５ｐｐｍとのピーク面積比よりフェノール性水酸基の含有量を求めたところ、滴定による結果と同様にフェノール性水酸基当量は１８０ｇ／ｅｑであった。
【００６２】
炭化水素アルコール（Ａ−２）の合成
炭化水素・フェノール樹脂（Ｐ−２）１８０ｇを用いた以外は、実施例１と同一の方法で反応を行ったところ、下式（１４）で表される目的とする淡黄色の炭化水素アルコール（Ａ−２）１８２ｇを得た。得られた誘導体の、水酸基当量を測定したところ１８７ｇ／ｅｑであった。
【００６３】
【化２４】

【００６４】
淡水素分析法による炭素、水素の含有量はそれぞれ８０．４％、１１．０％、酸素定量法による酸素の含有量は８．６％であった。
得られた樹脂のＦＤマススペクトルを測定したところ分子量３６０、６０６、８５２、１０９８、１３４４のピークが検出された。
得られた誘導体の、水酸基当量を測定したところ１８６ｇ／ｅｑであった。
また、 ¹Ｈ−ＮＭＲ分析では、δ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンが多重線で観測されたが、炭素−炭素二重結合に起因するプロトンの吸収は認められず、δ ６．５〜７．５ｐｐｍの芳香環に結合したプロトンが消失しており、水素化が完了したことが確認された。
ＩＲによる分析においても（Ｐ−１）では３０５０ｃｍ^-1付近に見られた芳香族のＣ−Ｈ伸縮に由来するピークが消失しており、得られた樹脂が目的とする淡黄色の炭化水素アルコール誘導体（Ａ−２）であることを確認した。
【００６５】
炭化水素エポキシ樹脂（Ｅ−２）の合成
上記の炭化水素アルコール（Ａ−２）のグリシジル化を以下の方法で行った。
攪拌機、還流冷却器および温度計付きの２リットル４つ口フラスコに炭化水素アルコール（Ａ−２）１８６ｇとエピクロルヒドリン７００ｇとを仕込んだ後、溶解、攪拌し、反応系内を１５０ｍｍＨｇの圧力に調製し、６８℃に昇温した。この系に濃度４８重量％の水酸化ナトリウム水溶液１００ｇを連続的に添加しながら３．５時間反応させた。該反応により生成する水および水酸化ナトリウム水溶液の水を、水−エピクロルヒドリン共沸混合物の還流により分解し、反応系外へ連続的に除去した。反応終了後、反応系を常圧に戻し１１０℃の温度まで昇温して反応系の水を完全に除去した。過剰のエピクロルヒドリンを常圧下で蒸留除去し、さらに１５ｍｍＨｇの減圧下に１４０℃で蒸留を行なった。
【００６６】
生成した樹脂および塩化ナトリウムの混合物に、メチルイソブチルケトン３００ｇおよび１０重量％の水酸化ナトリウム水溶液３６ｇを加え、８５℃の温度で１．５時間反応を行なった。反応終了後、メチルイソブチルケトン７５０ｇおよび水３００ｇを加え、下層の塩化ナトリウム水溶液を分液除去した。次にメチルイソブチルケトン液層に水１５０ｇを加えて洗浄し、リン酸で中和し、水層を分離したのちさらに水８００ｇで洗浄し水層を分離した。次いで、メチルイソブチルケトン液層を常圧下で蒸留したのち、５ｍｍＨｇ、１４０℃で減圧蒸留を行い、２１０ｇの下式（１５）で表される炭化水素エポキシ樹脂（Ｅ−２）を得た。このエポキシ樹脂のエポキシ当量は２７５ｇ／当量であった。
【００６７】
【化２５】

【００６８】
［合成例３］
炭化水素・フェノール樹脂（Ｐ−３）の合成
ジシクロペンタジエンの代わりにテトラヒドロインデンを３７０ｇ用いた以外は、実施例１と同様に反応、精製を行い、下式（１６）で表わされるフェノール樹脂（Ｐ―３）５５０ｇを得た。
【００６９】
【化２６】

【００７０】
得られたフェノール樹脂（Ｐ−３）は、軟化点が９３℃、ガードナー色相は１２、残存ホウ素は５ｐｐｍ、フッ素は３ｐｐｍ以下であった。フェノール性水酸基当量は１８３ｇ／ｅｑであった。
炭水素分析法による炭素、水素の含有量はそれぞれ、８２．２％、７．９％、酸素定量法による酸素の含有量は９．９％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量３０８、５２２、７３４、９４９のピークが検出され、式（１６）に示した構造の分子で構成されていることが確認された。
フェノール性水酸基の含有量を、無水酢酸でアセチル化した後、逆滴定により求めたところ、フェノール性水酸基当量は１７０ｇ／ｅｑであった。
¹Ｈ−ＮＭＲ分析では、δ ６．５〜７．５ｐｐｍに芳香環に結合したプロトンが、またδ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンがそれぞれ多重線で観測され、炭素−炭素二重結合に起因するプロトンの吸収は認められなかった。またδ ６．５〜８ｐｐｍとδ ０．８〜２．５ｐｐｍとのピーク面積比よりフェノール性水酸基の含有量を求めたところ、滴定による結果と同様にフェノール性水酸基当量は１８３ｇ／ｅｑであった。
また、¹³Ｃ−ＮＭＲ分析では、フェノールが二重結合にエーテル付加した場合に生じる１５８ｐｐｍの炭素のシグナルが観測され、エーテル化比率は１０％であった。
【００７１】
炭化水素アルコール（Ａ−３）の合成
フェノール樹脂（Ｐ−３）１８３ｇ、イソプロパノール４００ｇ、ラネーニッケル１０．０ｇを仕込んだ以外は実施例１と同様に反応を行い、下式（１７）で表される目的とする淡黄色の炭化水素アルコール（Ａ−３）１８９ｇを得た。
【００７２】
【化２７】

【００７３】
淡水素分析法による炭素、水素の含有量はそれぞれ７９．３％、１１．２％、酸素定量法による酸素の含有量は９．６％であった。
得られた樹脂のＦＤマススペクトルを測定したところ分子量３２０、５４０、７６０、９８０、のピークが検出された。
得られた誘導体の、水酸基当量を測定したところ１８８ｇ／ｅｑであった。
また、 ¹Ｈ−ＮＭＲ分析では、δ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンが多重線で観測されたが、炭素−炭素二重結合に起因するプロトンの吸収は認められず、δ ６．５〜７．５ｐｐｍの芳香環に結合したプロトンが消失しており、水素化が完了したことが確認された。
¹³Ｃ−ＮＭＲ分析では、環状の脂肪族炭化水素にエーテル付加した場合に生じる６８ｐｐｍの炭素のシグナルが観測され、エーテル化比率は１０％であった。
ＩＲによる分析においてもＰ−１では３０５０ｃｍ^-1付近に見られた芳香族のＣ−Ｈ伸縮に由来するピークが消失しており、得られた樹脂が目的とする淡黄色の炭化水素アルコール誘導体（Ａ−３）であることを確認した。
¹³Ｃ−ＮＭＲ分析では、フェノールが二重結合にエーテル付加した場合に生じる１５８ｐｐｍの炭素のシグナルが観測され、エーテル化比率は１０％であった。
【００７４】
炭化水素エポキシ樹脂（Ｅ−３）の合成
上記の炭化水素アルコール（Ａ−３）のグリシジル化を以下の方法で行った。
攪拌機、還流冷却器および温度計付きの２リットル４つ口フラスコに、炭化水素アルコール（Ａ−３）１８８ｇとエピクロルヒドリン７００ｇとを仕込んだ後、実施例１と同様に反応後、後処理を行い、２６０ｇの下式（１８）で表される炭化水素エポキシ樹脂（Ｅ−３）を得た。このエポキシ樹脂のエポキシ当量は２７０ｇ／当量であった。
【００７５】
【化２８】

【００７６】
［合成例４］
炭化水素・フェノール樹脂（Ｐ−４）の合成
フェノール２０００ｇとトルエン４００ｇとを、還流冷却器及びリービッヒコンデンサーを備えた容量５リットルの反応器に仕込み、１７０℃に加熱して、トルエン３５０ｇを留出し、反応系内の水分含有量を７０ｐｐｍとした。次いで、反応系を７０℃まで冷却し、三フッ化ホウ素・フェノール錯体１０ｇを添加した後、反応温度を７０℃に制御しながら、水分含有量が２０ｐｐｍのイソプレン３６０ｇを１．５時間かけて徐々に滴下し、滴下終了後、１００℃で５時間反応を行った。反応終了後、得られた反応物にＭｇ_0.7 Ａｌ_0.3 （ＯＨ）₂ （ＣＯ₃ ）_0.15・ｍＨ₂ Ｏ（但し、０．４６≦ｍ≦０．５４）で表されるハイドロタルサイト化合物（協和化学工業社製合成ハイドロタルサイト・商品名「 ＫＷ−１０００」）１５ｇ添加し、３０分間攪拌して触媒を失活させた後、セライトを敷き詰めたろ紙を用いて反応液をろ過した。得られた反応液を２００℃で薄膜蒸留を行い、蒸留留分として４００ｇの液状のフェノール樹脂を得た。この樹脂中のフェノール残量を測定したところ１０ｐｐｍであった。
【００７７】
得られたフェノール樹脂（Ｐ−４）は、残存ホウ素５ｐｐｍ、フッ素は３ｐｐｍ以下であった。１５０℃のおける溶融粘度は０．１５ｐｏｉｓｅであった。フェノール性水酸基当量は１５５であった。
炭水素分析法による炭素、水素の含有量はそれぞれ、８０．７％、８．９％、酸素定量法による酸素の含有量は１０．５％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量２５６、３２６のピークが検出され、下式（１９）に示した構造の分子で構成されていることが確認された。
【００７８】
【化２９】

【００７９】
フェノール性水酸基の含有量を、無水酢酸でアセチル化した後、逆滴定により求めたところ、フェノール性水酸基当量は１５５ｇ／ｅｑであった。
¹Ｈ−ＮＭＲ分析では、δ ６．５〜７．５ｐｐｍに芳香環に結合したプロトンが、またδ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンがそれぞれ多重線で観測され、炭素−炭素二重結合に起因するプロトンの吸収は認められなかった。またδ ６．５〜８ｐｐｍとδ ０．８〜２．５ｐｐｍとのピーク面積比よりフェノール性水酸基の含有量を求めたところ、滴定による結果と同様にフェノール性水酸基当量は１５５ｇ／ｅｑであった。
また、¹³Ｃ−ＮＭＲ分析では、フェノールが二重結合にエーテル付加した場合に生じる１５８ｐｐｍの炭素のシグナルが観測されないことからフェノールはいずれもアルキレーションで付加していることがわかった。
【００８０】
炭化水素アルコール（Ａ−４）の合成
上記のフェノール樹脂（Ｐ−４）１５５ｇを用いた以外は、実施例１と同一の方法で反応を行ったところ、目的とする淡黄色の炭化水素アルコール（Ａ−４）１５９ｇを得た。
【００８１】
淡水素分析法による炭素、水素の含有量はそれぞれ、７７．７％、１２．３％、酸素定量法による酸素の含有量は１０．１％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量２６８、３３８のピークが検出された。
得られた誘導体の、水酸基当量を測定したところ１６１ｇ／ｅｑであった。
また、 ¹Ｈ−ＮＭＲ分析では、δ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンが多重線で観測されたが、炭素−炭素二重結合に起因するプロトンの吸収は認められず、δ ６．５〜７．５ｐｐｍの芳香環に結合したプロトンが消失しており、水素化が完了したことが確認された。
ＩＲによる分析においてもＰ−１では３０５０ｃｍ^-1付近に見られた芳香族のＣ−Ｈ伸縮に由来するピークが消失しており、得られた樹脂が下式（２０）で示される目的とする淡黄色の炭化水素アルコール誘導体（Ａ−４）であることを確認した。
【００８２】
【化３０】

【００８３】
炭化水素エポキシ樹脂（Ｅ−４）の合成
上記の炭化水素アルコール（Ａ−４）のグリシジル化を以下の方法で行った。
攪拌機、還流冷却器および温度計付きの２リットル４つ口フラスコに、炭化水素アルコール（Ａ−４）１６１ｇとエピクロルヒドリン７００ｇとを仕込んだ後、実施例１と同様に反応後、後処理を行い、下式（２１）で示される２２０ｇの炭化水素エポキシ樹脂（Ｅ−４）を得た。このエポキシ樹脂のエポキシ当量は２４５ｇ／当量であった。
【００８４】
【化３１】

【００８５】
［合成例５］
炭化水素・フェノール樹脂（Ｐ−５）の合成
フェノール２０００ｇとトルエン４００ｇとを、還流冷却器及びリービッヒコンデンサーを備えた容量５リットルの反応器に仕込み、１７０℃に加熱して、トルエン３５０ｇを留出し、反応系内の水分含有量を７０ｐｐｍとした。次いで、反応系を７０℃まで冷却し、三フッ化ホウ素・フェノール錯体１０ｇを添加した後、反応温度を７０℃に制御しながら、水分含有量が２０ｐｐｍのリモネン４１０ｇを１．５時間かけて徐々に滴下し、滴下終了後、１００℃で５時間反応を行った。反応終了後、得られた反応物にＭｇ_0.7 Ａｌ_0.3 （ＯＨ）₂ （ＣＯ₃ ）_0.15・ｍＨ₂ Ｏ（但し、０．４６≦ｍ≦０．５４）で表されるハイドロタルサイト化合物（協和化学工業社製合成ハイドロタルサイト・商品名「ＫＷ−１０００」）１５ｇ添加し、３０分間攪拌して触媒を失活させた後、セライトを敷き詰めたろ紙を用いて反応液をろ過した。得られた反応液を２００℃で薄膜蒸留を行い、蒸留留分として５７０ｇのフェノール樹脂（Ｐ―５）を得た。この樹脂中のフェノール残量を測定したところ１０ｐｐｍであった。
【００８６】
得られたフェノール樹脂（Ｐ−５）は、軟化点が９３℃、ガードナー色相は１２、残存ホウ素は５ｐｐｍ、フッ素は３ｐｐｍ以下であった。
炭水素分析法による炭素、水素の含有量はそれぞれ、８１．５％、８．６％、酸素定量法による酸素の含有量は１０．０％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量３２４のピークが検出され、下式（２２）に示した構造の分子（ｎ＝０）で構成されていることが確認された。
【００８７】
【化３２】

【００８８】
フェノール性水酸基の含有量を、無水酢酸でアセチル化した後、逆滴定により求めたところ、フェノール性水酸基当量は１６１ｇ／ｅｑであった。
¹Ｈ−ＮＭＲ分析では、δ ６．５〜７．５ｐｐｍに芳香環に結合したプロトンが、またδ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンがそれぞれ多重線で観測され、炭素−炭素二重結合に起因するプロトンの吸収は認められなかった。またδ ６．５〜８ｐｐｍとδ ０．８〜２．５ｐｐｍとのピーク面積比よりフェノール性水酸基の含有量を求めたところ、滴定による結果と同様にフェノール性水酸基当量は１６１ｇ／ｅｑであった。
また、¹³Ｃ−ＮＭＲ分析では、フェノールが二重結合にエーテル付加した場合に生じる１５８ｐｐｍの炭素のシグナルが観測されないことからフェノールはいずれもアルキレーションで付加していることがわかった。
【００８９】
炭化水素アルコール（Ａ−５）の合成
上記のフェノール樹脂（Ｐ−５）１６１ｇを用いた以外は、実施例１と同一の方法で反応を行ったところ、下式（２３）に示した目的とする淡黄色の炭化水素アルコール（Ａ−５）１６３ｇを得た。
【００９０】
【化３３】

【００９１】
また、 ¹Ｈ−ＮＭＲ分析では、δ ６．５〜７．５ｐｐｍの芳香環に結合したプロトンが消失しており、水素化が完了したことが確認された。
淡水素分析法による炭素、水素の含有量はそれぞれ７８．６％、１１．９％、酸素定量法による酸素の含有量は９．６％であった。
得られた樹脂のＦＤマススペクトルを測定したところ、分子量３３６のピークが検出された。
得られた誘導体の、水酸基当量を測定したところ１６８ｇ／ｅｑであった。
また、 ¹Ｈ−ＮＭＲ分析では、δ ０．８〜４．０ｐｐｍに脂肪族炭化水素環に由来するプロトンが多重線で観測されたが、炭素−炭素二重結合に起因するプロトンの吸収は認められず、δ ６．５〜７．５ｐｐｍの芳香環に結合したプロトンが消失しており、水素化が完了したことが確認された。
ＩＲによる分析においてもＰ−１では３０５０ｃｍ^-1付近に見られた芳香族のＣ−Ｈ伸縮に由来するピークが消失しており、得られた樹脂が目的とする淡黄色の炭化水素アルコール誘導体（Ａ−１）であることを確認した。
【００９２】
炭化水素エポキシ樹脂（Ｅ−５）の合成
上記の炭化水素アルコール（Ａ−５）のグリシジル化を以下の方法で行った。攪拌機、還流冷却器および温度計付きの２リットル４つ口フラスコに、炭化水素アルコール（Ａ−５）１６８ｇとエピクロルヒドリン７００ｇとを仕込んだ後、実施例１と同様に反応後、後処理を行い、下式（２４）で示される２１０ｇの炭化水素エポキシ樹脂（Ｅ−５）を得た。このエポキシ樹脂のエポキシ当量は２５０ｇ／当量であった。
【００９３】
【化３４】

【００９４】
（実施例１）
合成例１で製造したエポキシ樹脂（Ｅ−１）７０ｇ、フェノールノボラック樹脂（荒川化学工業（株）製、商品名「タマノール７５８」）３０ｇ、トリフェニルホスフィン０．２ｇ、溶融シリカ粉末（商品名「ヒュウズレックスＲＤ−８」、龍森（株）社製）３５３ｇ及び表１に示す添加剤からなる組成物を調製し、該組成物を、ニーダーを用いて８５℃にて１０分間溶融混練し、冷却後粉砕してエポキシ樹脂成型材料を得た。
得られた成型材料をタブレット化し、該タブレット化した成型材料を低圧トランスファー成型機にて１７５℃、７０ｋｇ／ｃｍ² 、１２０秒の条件で封止した後、１８０℃、５時間の条件で後硬化させた。尚、トランスファー成型時の離型性は良好であった。得られた硬化物を用い、半田クラック試験用としては、６×６ｍｍのチップを５２ｐパッケージに封止し、また半田耐湿試験用としては６×６ｍｍのチップを１６ｐＳＯＰパッケージに封止してテスト用素子を作製した。封止したテスト用素子について下記の半田クラック試験及び半田耐湿試験を行った。結果を表１に示す。
【００９５】
（半田クラック試験）；封止したテスト用素子を８５℃、８５％ＲＨの環境下で４８時間および７２時間処理し、その後２８０℃の半田槽に１０秒間浸漬後顕微鏡で外部クラックを観察した。
（半田耐湿性平均寿命（時間））；封止したテスト用素子を８５℃、８５％ＲＨの環境下で４８時間および７２時間処理し、その後２８０℃の半田槽に１０秒間浸漬後プレッシャークッカー試験（１２５℃、１００％ＲＨ）を行い５０％の回路のオーブン不良が発生するまでの時間を測定した。
【００９６】
（実施例２〜５）
エポキシ樹脂（Ｅ−１）の代わりに合成例２〜５で製造したエポキシ樹脂（Ｅ−２）、（Ｅ−３）、（Ｅ−４）、（Ｅ−５）を用いた以外は実施例１と同様にして成型材料を得、各試験を行った。その結果を表１に示す。
【００９７】
（比較例１）
エポキシ樹脂（Ｅ−１）をノボラックエポキシ樹脂（商品名「エピクロンＮ−６６０」、大日本インキ化学工業（株）製）６８ｇに代え、表１に示す配合割合とした以外は実施例１と同様にして成型材料を得、試験を行った。結果を表１に示す。
【００９８】
【表１】

【００９９】
（実施例６）
合成例１で製造したエポキシ樹脂（Ｅ−１）および表２に示す市販のフェノール樹脂に、表２に示す硬化促進剤を配合してエポキシ樹脂組成物を得、ついで表２に示す溶剤を配合して、エポキシ樹脂ワニス（樹脂成分が６０重量％）とした後、該エポキシ樹脂ワニス中に、Ｅガラス布を浸漬した。このワニス含浸布を１６０℃の乾燥室中で４分間乾燥させ、Ｂステージ状のプリプレグを得た。
得られたプリプレグを切断して８枚のプリプレグとし、更に８枚のプリプレグを重ね合わせ、その両面に厚さ３５μｍの電解銅箔２枚を重ねて、４０ｋｇ／ｃｍ² で加圧しながら１７５℃で１２０分加圧加熱して積層板とした。得られた硬化積層板の物性を表２に示す。
【０１００】
（実施例７〜１０）
エポキシ樹脂（Ｅ−１）の代わりに、実施例２〜５で製造したフェノール樹脂（Ｅ−２）、（Ｅ−３）、（Ｅ−４）、（Ｅ−５）を用いた以外は実施例６と同様にして積層板を作成した。試験結果を表２に示す。
【０１０１】
（比較例２）
エポキシ樹脂（Ｅ−１）をノボラックエポキシ樹脂（商品名「エピクロンＮ−６６０」、大日本インキ化学工業（株）製）６８ｇに代え、表２に示す配合割合とした以外は実施例６と同様にして積層板を作成した。試験結果を表２に示す。
【０１０２】
【表２】

【０１０３】
【発明の効果】
本発明の炭化水素アルコールは炭化水素基を結節基とし、芳香環が水素化された脂環構造を有する飽和炭化水素アルコールであり、結節基が鎖状の炭化水素基の場合、溶解性、反応性、熱安定性に優れ、柔軟性、耐熱性、耐候性に優れたエポキシ樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂の原料として最適である。これに対して、結節基が剛直でかさ高い環状炭化水素基の場合、耐湿性、耐熱性および電気特性に優れた前記の各樹脂の原料として最適である。また、これらの樹脂は感光剤をはじめとする各種工業用品の原料、各種高分子材料の添加剤としても有用である。
【０１０４】
本発明のエポキシ樹脂を使用した組成物は、半導体封止材用、積層板用およびソルダーレジスト用エポキシ樹脂組成物として好ましい特性を備えている。
例えば、半導体封止材用として使用する場合、得られる硬化物の耐湿性が非常に良好で、またガラス転移点が高いため耐熱性に優れている。従って硬化物は耐熱性に優れており、リード線の半田付けの際に半導体パッケージが急激な温度変化を受けても、樹脂成形部にクラックが生じたり、リード線と樹脂との間の界面が劣化したりすることがまったくなく、更には機械的物性や電気特性等にも優れている。
【０１０５】
また本発明のエポキシ樹脂を使用した組成物は、耐熱性、接着性および耐湿性等に優れているので、積層板用エポキシ樹脂組成物として用いる場合、遠赤外線、赤外線、ハンダ付け等による加熱によって生じるミーズリング現象や相間剥離が生じることがなく、更には反りが極めて少なく、寸法安定性、スルーホールの接着信頼性に優れ、ドリル加工性も良好にすることができる。さらに本発明のエポキシ樹脂を使用した組成物を用いると、電気特性に優れた積層板を製造できるという特徴を有する。すなわち高速電子機器用、高周波機器用プリント基板を製造するためには誘電特性を向上させることが必須であり、誘電特性は使用するエポキシ樹脂の構造に依存することが知られているが、本発明によるエポキシ樹脂組成物を使用した積層板は、誘電特性が非常に優れている。
【０１０６】
本発明のエポキシ樹脂を使用した組成物をソルダーレジストに用いる場合、密着性、電気絶縁性および耐電触性、はんだ耐熱性、レベラー用水溶性フラックスに対する非白化性、塩化メチレン等の溶剤に対する優れた耐性、耐酸および耐アルカリ性、耐メッキ性、ＰＣＴ性等に優れる。
【０１０７】
本発明の製造法により、上記炭化水素アルコール、上記炭化水素エポキシ樹脂を容易に製造できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel hydrocarbon alcohol optimum as various resin raw materials and additives, a hydrocarbon epoxy resin derived from the hydrocarbon alcohol, and a process for producing each resin. More specifically, the present invention relates to a hydrocarbon alcohol having a saturated hydrocarbon group as a nodule group and a hydroxyl group-containing saturated cyclic hydrocarbon group as a repeating unit, and an epoxy resin derived from the hydrocarbon alcohol. Further, the present invention nucleates the hydroxyphenyl group of a specific hydrocarbon / phenol resin obtained by an alkylation reaction between a specific phenol and an unsaturated hydrocarbon having two or more carbon-carbon double bonds. The present invention relates to a method for producing a hydrocarbon alcohol, and a method for producing a hydrocarbon epoxy resin, characterized in that the hydrocarbon alcohol is glycidylated.
[0002]
[Prior art]
An alicyclic polyhydric alcohol having a plurality of hydroxyl groups in the molecule has been utilized in various fields as a resin raw material and a resin modifying component.
For example, hydrogenated bisphenols, which are hydrogenated products of bisphenols, are a kind of alicyclic dihydric alcohols. Hydrogenated bisphenol-A obtained by hydrogenating bisphenol-A contains phthalic acid, When polycondensed with a dibasic acid such as maleic acid or adipic acid, it becomes a polyester resin having heat resistance and moisture resistance, and has been put to practical use as various materials.
[0003]
A compound obtained by reacting hydrogenated bisphenol-A with epichlorohydrin has been commercialized as an alicyclic epoxy resin having an epoxy group at the terminal, and is regarded as a material for outdoor weather-resistant powder coating materials because of its good weather resistance. Yes. The epoxy resin is also used in the electronics industry as a low-viscosity epoxy resin having excellent electrical characteristics.
Other hydrogenated bisphenols and hydrogenated trisphenols are also used in similar applications.
[0004]
[Problems to be solved by the invention]
Advances in science and technology centering on the electronics industry are remarkable, and the requirements for each product and its raw materials are becoming more and more severe. The above-mentioned hydrogenated bisphenols, hydrogenated trisphenols, and these alicyclic alcohols are used as raw materials. The polyester resins and epoxy resins that have been developed have problems of being unable to satisfy moisture resistance, weather resistance, heat resistance, and electrical properties, and novel alicyclic polyfunctional alcohols and alicyclics that can solve these problems. Development of a polyfunctional epoxy resin is awaited.
For example, epoxy resins derived from these alicyclic polyhydric alcohols have been used for powder coatings, etc., but it has been pointed out that the weather resistance, water resistance, dispersibility, etc. are poor and there are many practical problems. It was.
[0005]
The inventors of the present invention 4-300916 And phenol / resin resins obtained by reacting phenols with unsaturated hydrocarbon compounds containing two or more carbon-carbon double bonds in Japanese Patent Application Laid-Open No. 7-17887. Has been proposed to use. The phenolic resin is excellent in solubility, reactivity and thermal stability when a chain unsaturated hydrocarbon such as butadiene or isoprene is used as an unsaturated hydrocarbon as a raw material, and cyclic unsaturated such as dicyclopentadiene or tetrahydroindene. When hydrocarbon is used, it becomes a hydrocarbon / phenolic resin with a structure in which hydroxyphenyl group is knotted with a bulky hydrophobic alicyclic saturated hydrocarbon group, so the cured product using this has moisture resistance, heat resistance and Excellent electrical characteristics.
[0006]
The first object of the present invention is to provide various resin raw materials such as epoxy resins, polyester resins, polycarbonate resins, polyurethane resins and the like which are also useful as raw materials for various industrial products including photoresists and additives for various polymer materials. It is to provide a novel hydrocarbon alcohol that is optimal as an additive, and a second object of the present invention is an excellent electrical property, heat resistance, and moisture resistance derived from the hydrocarbon alcohol, a printed wiring board, It is to provide a hydrocarbon epoxy resin that is useful as a raw material for electronic component sealing materials, paints, and various sealing materials, and a third object of the present invention is to provide a production method that can easily produce these resins. It is.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to develop a hydrocarbon alcohol that has solved the disadvantages of the conventional alicyclic polyhydric alcohol described above, the hydrocarbon-phenolic resin is catalytically hydrogenated in the presence of a metal catalyst. The inventors have found that the present invention can be a novel hydrocarbon alcohol that is promising as a raw material for epoxy resins and polyester resins that can improve moisture resistance, heat resistance, and weather resistance.
[0008]
That is, the invention of claim 1 of the present invention has the general formula (1).
[Chemical 9]
hc- (R1 -hc) n-R1 -hc
(In the formula, hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups are directly bonded to the saturated cyclic hydrocarbon group. R1 represents the number of carbon atoms. (It is a saturated hydrocarbon group of 4 to 25. Note that two hc linked to R1 are not bonded to the same carbon in R1. N is 0 or an integer of 1 to 30.)
It is related with the hydrocarbon alcohol represented by these.
[0009]
The invention of claim 2 of the present invention has the general formula (2)
[Chemical Formula 10]
hc- (R2 -hc) n-R2 -hc
(In the formula, hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups in hc are directly bonded to the cyclic saturated hydrocarbon group. R2 has 5 carbon atoms. A saturated polycyclic hydrocarbon group of ˜25, wherein the two hc linked to R2 are not bonded to the same carbon in R2.n is 0 or an integer of 1-30.)
It is related with the hydrocarbon alcohol represented by these.
[0010]
The invention of claim 3 of the present invention has the general formula (3)
Embedded image
hp- (R1 -hp) n-R1 -hp
(In the formula, hp represents a polyhydroxyphenyl group having 6 to 16 carbon atoms. The hydroxyl group in hp is a phenolic hydroxyl group, and 1 to 3 are bonded to hp. The phenolic hydroxyl group is 1 to 3 in number. R1 is a hydrocarbon group having 4 to 25 carbon atoms, wherein two hps linked to R1 are not bonded to the same carbon in R1, and n is an integer of 0 or 1-30. )
The hydrocarbon / phenol resin represented by the formula (1) is hydrogenated in the presence of a metal catalyst.
[0011]
The invention of claim 4 of the present invention is general formula (4).
Embedded image
hp- (R2-hp) n-R2-hp
(In the formula, hp represents a polyhydroxyphenyl group having 6 to 16 carbon atoms. The number of phenolic hydroxyl groups in hp is 1 to 3. R2 is a polycyclic hydrocarbon group having 5 to 25 carbon atoms. Note that two hps connected to R2 are not bonded to the same carbon in R2, and n is 0 or an integer of 1 to 30.)
The method according to claim 2, wherein the hydrocarbon / phenol resin represented by the formula (1) is hydrogenated in the presence of a metal catalyst.
[0012]
The invention of claim 5 of the present invention is general formula (5).
Embedded image
gc- (R1 -gc) n-R1 -gc
(In the formula, gc represents an X—O— group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. X represents a glycidyl group, and the number of X—O— groups in gc is 1 to 3. Directly bonded to a saturated cyclic hydrocarbon group, R1 is a saturated hydrocarbon group having 4 to 25 carbon atoms, and two gc linked to R1 are not bonded to the same carbon in R1. 0 or an integer of 1 to 30).
[0013]
The invention of claim 6 of the present invention is general formula (6).
Embedded image
gc- (R2 -gc) n-R2 -gc
(In the formula, gc represents an X—O— group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. X represents a glycidyl group, and the number of X—O— groups in gc is 1 to 3. Directly bonded to a saturated cyclic hydrocarbon group R2 is a saturated polycyclic hydrocarbon group having 5 to 25 carbon atoms, and two gc linked to R2 are not bonded to the same carbon in R2. N is 0 or an integer from 1 to 30.)
It is related with the hydrocarbon epoxy resin represented by these.
[0014]
The invention of claim 7 of the present invention provides the general formula (1).
Embedded image
hc- (R1 -hc) n-R1 -hc
(In the formula, hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups are directly bonded to the saturated cyclic hydrocarbon group. R1 represents the number of carbon atoms. (It is a saturated hydrocarbon group of 4 to 25. Note that two hc linked to R1 are not bonded to the same carbon in R1. N is 0 or an integer of 1 to 30.)
The method according to claim 5, wherein the hydrocarbon alcohol represented by the formula (1) is reacted with epihalohydrin in the presence of a base.
[0015]
The invention of claim 8 of the present invention provides the general formula (2).
Embedded image
hc- (R2-hc) n-R2-hc
(Wherein hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups in hc are directly bonded to the saturated cyclic hydrocarbon group. R2 has 5 carbon atoms. A saturated polycyclic hydrocarbon group of ˜25, wherein two gc's connected to R2 are not bonded to the same carbon in R2.n is 0 or an integer of 1-30.)
The hydrocarbon alcohol represented by these and epihalohydrin are made to react in base presence, It is related with the manufacturing method of the hydrocarbon epoxy resin of Claim 6.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is further described below.
The hydrocarbon alcohol obtained in the present invention is an alicyclic polyhydric alcohol having a structure in which a hydroxyl group-containing saturated cyclic hydrocarbon group is knotted with a saturated hydrocarbon group, and is more resistant to weathering and moisture than conventional hydrogenated bisphenols. It has excellent properties such as heat resistance and electrical properties, and is useful as a raw material for polyester resins and epoxy resins.
The reason for this is that conventional alicyclic polyhydric alcohols are produced by using phenols and aldehydes as binders for the raw material phenol resins. Whereas the hydroxyalkane skeleton has a 1,1-bishydroxyalkane structure bonded to the same carbon, the hydrocarbon alcohol of the present invention has a hydroxyalkane skeleton bonded to a different carbon, so that the thermal stability, It is because it is excellent in oxidation resistance.
When the knot group is a chain hydrocarbon group, the hydrocarbon alcohol of the present invention has characteristics of lower viscosity and lower hygroscopicity than conventional alicyclic polyhydric alcohols. On the other hand, when the nodule group is a polycyclic saturated hydrocarbon, a cured product using this as a raw material has a high glass transition temperature and is excellent in heat resistance, moisture resistance, and electrical characteristics. Hydrocarbon epoxy resins derived from the hydrocarbon alcohols have similar characteristics not found in conventional alicyclic epoxy resins.
Specific examples of these hydrocarbon alcohols and epoxy resins derived therefrom include compounds represented by the following formulas (7) to (9). In each formula, when A is hydrogen, it is a hydrocarbon alcohol, and when A is a glycidyl group, it is a hydrocarbon epoxy resin.
[0017]
Embedded image

[0018]
Embedded image

[0019]
Embedded image

[0020]
The hydrocarbon alcohol of the present invention is produced by a nuclear hydrogenation reaction of a hydrocarbon / phenol resin.
The raw material hydrocarbon / phenol resin can be produced by the following method.
That is, in the presence of an acid catalyst, a phenol having 6 to 16 carbon atoms having 1 to 3 phenolic hydroxyl groups and an unsaturated hydrocarbon having 4 to 25 carbon atoms having two or more carbon-carbon double bonds are obtained. Produced by reacting.
[0021]
Examples of the unsaturated hydrocarbon include acyclic polyenes having 4 to 25 carbon atoms such as isoprene, butadiene, piperylene, hexadiene and octatriene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, cyclooctadiene, limonene, pinene and vinyl. Cyclohexene, vinyl norbornene, tetrahydroindene, dicyclopentadiene, methyl dicyclopentadiene and other alicyclic unsaturated hydrocarbons having 5 to 25 carbon atoms, aromatic dienes such as divinylbenzene, and dials of these unsaturated hydrocarbons Mention may be made of Alder reaction products. In use, it can be used alone or as a mixture.
[0022]
Many of these compounds are raw materials, intermediate raw materials or by-products in the production plant of 5-ethylidene norbornene, which is the third component of EPDM (ethylene propylene diene methylene rubber), and are industrially available at low cost. be able to.
[0023]
When hydrocarbon or phenol resin is desired to have a cyclic hydrocarbon group as a nodule group, the unsaturated hydrocarbon of the raw material is usually a cyclic hydrocarbon, but an acyclic unsaturated hydrocarbon such as octatriene is usually used. Even if it uses, a cyclization reaction occurs with an alkylation reaction, and a desired cyclic hydrocarbon and phenol resin can be manufactured.
[0024]
Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-propylphenol, and p-propylphenol. , Monohydric phenol such as p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, α-naphthol, β-naphthol Resorcinol, catechol, hydroquinone, 2,2-bis (4′-hydroxyphenyl) propane, 1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane, tetramethylbiphenol, Preferable examples include dihydric phenols such as biphenol; trihydric phenols such as trishydroxyphenylmethane and mixtures thereof. In particular, phenol, o-cresol, m-cresol, α-naphthol, β-naphthol, 2,2-bis (4′-hydroxyphenyl) propane and the like are desirable from the viewpoints of economy and ease of production.
[0025]
The charging ratio of the phenols to the hydrocarbon is desirably 0.8 to 12 times, preferably 1 to 8 times, molar equivalent of the phenols with respect to the hydrocarbon. When the charging ratio of the phenols is less than 0.8 times molar equivalent, the homopolymerization of the hydrocarbon occurs simultaneously, and when it exceeds 12 times molar equivalents, it becomes difficult to recover unreacted phenols. Therefore, it is not preferable.
[0026]
Examples of the acid catalyst used when the phenols and the hydrocarbon are reacted include boron trifluoride; boron trifluoride complexes such as boron trifluoride ether complexes, water complexes, amine complexes, phenol complexes, and alcohol complexes. Aluminum compounds such as aluminum trichloride and diethylaluminum monochloride; iron chloride; titanium tetrachloride; sulfuric acid; hydrogen fluoride; trifluoromethanesulfonic acid and the like can be preferably used. From the viewpoint, boron trifluoride and boron trifluoride complex are preferable, and boron trifluoride and boron trifluoride / phenol complex are most preferable.
[0027]
The amount of the acid catalyst to be used is not particularly limited and can be appropriately selected depending on the catalyst to be used. For example, in the case of boron trifluoride / phenol complex, it is 0.1% with respect to 100 parts by weight of hydrocarbon. -20 parts by weight, preferably 0.5-10 parts by weight.
[0028]
The reaction between the phenols and the hydrocarbon can be carried out with or without a solvent. When no solvent is used, the phenols are used in an equimolar equivalent or more with respect to the hydrocarbon. It is preferable to use 3 to 12 times molar equivalent. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit the reaction, and particularly preferable solvents include aromatic hydrocarbon compounds such as benzene, toluene and xylene.
[0029]
The reaction temperature of the reaction varies depending on the type of acid catalyst to be used. For example, when boron trifluoride / phenol complex is used, it is usually 20 to 170 ° C., preferably 50 to 150 ° C. When the reaction temperature exceeds 170 ° C., decomposition or side reaction of the catalyst occurs. When the reaction temperature is less than 20 ° C., the reaction takes a long time and is disadvantageous economically.
[0030]
In the reaction, in order to make the reaction proceed smoothly, it is preferable to reduce the water in the system as much as possible, and it is particularly preferable to keep it at 100 ppm by weight or less. Further, in the reaction, it is preferable to carry out the polymerization while sequentially adding the hydrocarbons from the viewpoint of preventing homopolymerization of the hydrocarbons and controlling the heat of reaction.
[0031]
In this production method, the catalyst is deactivated after completion of the reaction.
The means for deactivation is not particularly limited, but it is preferable in terms of synthesis to use a means such that the residual amount of ionic impurities such as boron and fluorine in the finally obtained resin is 100 ppm or less.
As reagents used for this purpose, alkali metals, alkaline earth metals or oxides thereof, hydroxides, carbonates, ammonium hydroxide, ammonia gas, and other inorganic bases can be used. It is preferable to use hydrotalcites which are simple and fast and have a small residual amount of ionic impurities after treatment.
In this production method, after deactivating and adsorbing the acid catalyst with hydrotalcites and the like, the hydrotalcite and the like adsorbing the acid catalyst are removed by filtration, and the reaction liquid containing no catalyst residue is recovered. Next, the reaction solution is concentrated by distillation to obtain a high purity hydrocarbon / phenol resin.
[0032]
Next, the manufacturing method of the hydrocarbon alcohol of this invention is demonstrated in detail.
Hydrocarbon alcohol can be produced by diluting the above-mentioned hydrocarbon / phenol resin in a solvent and catalytic hydrogenation using a metal catalyst.
First, the aforementioned phenol resins are diluted in a solvent. The solvent used for dilution is not particularly limited, but lower alcohols such as methanol, ethanol, isopropanol, and isobutanol are suitable. Among them, isopropanol and isobutanol are preferable because of high activity.
The amount of the solvent used is not particularly limited, but is usually selected within a range of 1 to 2 times the weight of the phenol resin as a raw material.
The hydrogenation reaction is performed by contacting a metal catalyst with a hydrocarbon / phenolic resin in a diluted solution.
[0033]
The metal catalyst to be used is not particularly limited, and can be appropriately selected according to the reaction time and conditions. For example, a nickel-based catalyst, a palladium-based catalyst, a ruthenium-based catalyst, a rhodium-based catalyst and the like can be preferably exemplified. Among them, it is particularly preferable to use a Raney nickel-based catalyst which is relatively inexpensive and easily available and has a high reaction activity. Raney nickel may be used alone, but a cocatalyst compound such as an alkaline earth metal hydroxide may be appropriately added to enhance the activity.
[0034]
The amount of Raney nickel used in the present invention is 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the starting phenol resin, but is not limited to this, and the reaction time In order to shorten the length, Raney nickel in a larger amount can be used.
Although the reaction conditions can be changed according to the activity, the reaction temperature is 80 to 220 ° C, preferably 100 ° C to 200 ° C, and the hydrogen pressure is 2 to 3 kg / cm. ² Any pressure may be used as long as it is above, but preferably 5 to 150 kg / cm. ² , More preferably 40-60 kg / cm ² Perform in the range.
The reaction is carried out in a high-pressure autoclave by supplying a predetermined amount of Raney nickel catalyst or palladium catalyst and, if necessary, alkaline earth metal hydroxide to the appropriately diluted raw material phenol resin, substituting the inside of the autoclave with hydrogen and stirring with heating. Do it. Since the hydrogen pressure decreases as the reaction proceeds, after confirming that the hydrogen pressure does not decrease while repeating the replenishment, the heating and stirring is stopped and the autoclave is cooled.
After completion of the reaction, the reaction mixture is filtered to recover the reaction liquid without any catalyst and catalyst residue, and the solvent is distilled and concentrated to distill off the solvent. Get.
[0035]
Concentration may be performed under normal pressure, reduced pressure, increased pressure, or a combination thereof. The concentration temperature is preferably 80 ° C to 300 ° C, more preferably 10 ° C to 270 ° C, and further preferably 130 ° C to 250 ° C. If the concentration temperature exceeds 300 ° C., decomposition of the resin, dehydration reaction and the like may occur at the same time. In addition, nitrogen or water vapor may be blown into the concentrating system in order to smoothly and quickly concentrate.
[0036]
The hydrocarbon alcohol of the present invention can be used as a raw material for a polyester resin, but is optimal as a raw material for an epoxy resin as described later. Moreover, since the resin half-esterified with α, β-acid anhydride into the hydrocarbon alcohol of the present invention and introduced with a carboxylic acid group does not absorb in the short wavelength region, it can be preferably used as a semiconductor resist material. In particular, hydrocarbon alcohols whose tether groups are saturated polycyclic hydrocarbon skeletons or their t-butyl esters do not absorb light at 190 to 300 nm and have high dry etching resistance. Therefore, resists for semiconductors, especially resists for ArF excimer lasers. Ideal as a raw material.
[0037]
The hydrocarbon epoxy resin of the present invention can be obtained by glycidylation of the hydrocarbon alcohol, and the glycidylation reaction can employ the same method as in the case of the alicyclic alcohol. Specifically, for example, in the presence of a base such as sodium hydroxide or potassium hydroxide, the hydrocarbon alcohol is usually treated with epichlorohydrin, epibromohydrin, etc. at a temperature of 10 to 150 ° C., preferably 30 to 80 ° C. It can be obtained by reacting with a glycidylating agent and washing with water and drying. In this case, the amount of the glycidylating agent used is preferably 2 to 20 times molar equivalent, particularly preferably 3 to 7 times molar equivalent, relative to the hydrocarbon alcohol.
In the reaction, the reaction can be caused to proceed faster by distilling off water by azeotropic distillation with a glycidylating agent under reduced pressure. Further, when the hydrocarbon epoxy resin of the present invention is used in the electronic field, sodium chloride produced as a by-product in the epoxy resin must be completely removed in the water washing step. At this time, after collecting the glycidylating agent by distillation and concentrating the reaction solution, the concentrate may be dissolved in a solvent and washed with water. Preferred examples of the solvent include methyl isobutyl ketone, cyclohexanone, benzene, butyl cellosolve and the like. The water-washed concentrate can be made into a hydrocarbon epoxy resin by heating and concentrating after washing with water.
[0038]
The content of epoxy groups in the epoxy resin is usually 200 to 500 g / gram equivalent, preferably 250 to 450 g / gram equivalent. When the epoxy group content is less than 500 g / gram equivalent, the crosslinking density becomes too low, which is not preferable.
[0039]
The conditions for using the hydrocarbon epoxy resin of the present invention as an epoxy resin composition will be described in detail below.
The epoxy resin composition of the present invention comprises (a) a curable epoxy resin including the above epoxy resin (hereinafter referred to as component (a)), (b) a phenol resin (hereinafter referred to as component (b)), and (c). It contains a curing accelerator (hereinafter referred to as “component (c)”) as an essential component.
[0040]
The curable epoxy resin used as the component (a) in the epoxy resin composition of the present invention is a resin having at least one, preferably two or more epoxy groups in the molecule, in addition to the novel hydrocarbon epoxy. For example, epoxy resins synthesized from epichlorohydrin and bisphenol A and novolac resins, alicyclic epoxy resins such as mono- or diepoxides such as dicyclopentadiene and vinylcyclohexene, tetramethylbisphenol diglycidyl ether, triglycidyl isocyanurate, tetraglycidyl diamino Special epoxy resins such as diphenylmethane and epoxy resins obtained by introducing halogen atoms such as chlorine atoms and bromine atoms into these epoxy resins can be mentioned. It can be used as the above mixture.
Moreover, a commercial item can also be used as said (a) component, for example as a novolak epoxy resin, a brand name "Epicron N-660" (Dainippon Ink Chemical Co., Ltd. product), "Sumiepoxy ESCN-195X" (Manufactured by Sumitomo Chemical Co., Ltd.), “QUATREX 2410” (manufactured by Dow Chemical Co., Ltd.), “EOCN-100” (manufactured by Nippon Kayaku Co., Ltd.), “YDCN-702P” (manufactured by Toto Kasei Co., Ltd.) As special epoxy resins, “YX-4000” (manufactured by Yuka Shell Epoxy Co., Ltd.), “EPICLON EXA-1514”, “EPICLONP-4032”, “EPICLON EXA-1857” (Dainippon Ink Chemical Co., Ltd.) ), “Epicoat 157S65”, “Epicoat YL933” (manufactured by Yuka Shell Epoxy Co., Ltd.), “VG-31” 1 "(manufactured by Mitsui Petrochemical Co., Ltd.), and the like.
[0041]
The phenol resin used as the component (b) in the epoxy resin composition of the present invention is not particularly limited, and preferably includes a phenol resin having a molecular weight of 268 to 2000 represented by the above general formula 1. Moreover, the said phenol resin can also use the thing which has not isolated the phenol resin and contains reactants other than a phenol resin as it is.
[0042]
As the curing accelerator of the component (c) used in the epoxy resin composition of the present invention, any accelerator may be used as long as it promotes the reaction between an epoxy group and a phenolic hydroxyl group. Tertiary phosphines, imidazoles, tertiary amines and the like can be used. Specifically, preferred examples of the tertiary phosphines include triethylphosphine, tributylphosphine, triphenylphosphine, and the like. Preferred examples of the tertiary amine include dimethylethanolamine, dimethylbenzylamine, 2,4,6-tris (dimethylamino) phenol, 1,8-diazabicyclo [5.4.0] undecene. it can. Examples of the imidazoles include 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-vinyl-2-methylimidazole, 1 -Propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Phenylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy It can be exemplified methylimidazole. Particularly preferable examples of the component (c) include 2-methylimidazole, diazabicycloundecene (DBU), triphenylphosphine, dimethylbenzylamine, and mixtures thereof.
[0043]
The blending ratio of each component (a) to (c) used in the epoxy resin composition of the present invention is preferably 20 to 180 parts by weight, more preferably 20 to 180 parts by weight, with respect to 100 parts by weight of component (a). 30-120 weight part, (c) component becomes like this. Preferably it is 0.01-7.0 weight part, More preferably, it is 0.5-5.0 weight part.
In addition to the components (a) to (c), the epoxy resin composition for semiconductor encapsulation of the present invention further contains (d) an inorganic filler (hereinafter referred to as component (d)) as an essential component. Features.
In the epoxy resin composition for semiconductor encapsulation of the present invention, as the components (a), (b) and (c) used as essential components, any of the resins and compounds mentioned in the epoxy resin composition is preferably used. be able to. Moreover, as an inorganic filler used as the component (d), generally a silica powder filler or the like can be preferably used. The silica powder filler may be used after being melted.
[0044]
The blending ratio of each component (a) to (d) used in the epoxy resin composition for semiconductor encapsulation of the present invention is preferably 20 to 180 parts by weight of component (b) with respect to 100 parts by weight of component (a). More preferably, it is 30-120 weight part, (c) component is preferably 0.01-7.0 weight part, More preferably, it is 0.5-5.0 weight part, Furthermore, the mixture ratio of (d) component Is preferably 50 to 90% by weight, more preferably 65 to 85% by weight, based on the entire epoxy resin composition for semiconductor encapsulation.
[0045]
The epoxy resin composition for semiconductor encapsulation of the present invention contains the components (a) to (d) as essential components, but if necessary, contains a phenol resin other than the component (b). You can also. Examples of the phenol resin other than the component (b) include trade names “Tamanol-758”, “Tamanol-759” (manufactured by Arakawa Chemical Co., Ltd.), “ECN-1280” (manufactured by Ciba Geigy Co., Ltd.), and the like. Novolak-type phenol resins, brominated novolak-type phenol resins, polyphenol compounds such as polyvinylphenol, brominated polyvinylphenol, tetrabromobisphenol A, and the like. The amount of the phenol resin other than the component (b) is preferably 100 parts by weight or less, particularly preferably 50 parts by weight or less with respect to 100 parts by weight of the component (b). If the amount used exceeds 100 parts by weight, the moisture resistance deteriorates, which is not preferable.
[0046]
The epoxy resin composition for semiconductor encapsulation of the present invention includes a silane coupling agent, a brominated epoxy resin, a flame retardant such as antimony trioxide and hexabromobenzene, a colorant such as carbon black and bengara, a natural wax, and a synthetic wax. Various additives such as a mold release agent such as silicon oil, and a low stress additive such as rubber can be appropriately blended.
[0047]
In order to prepare a molding material using the epoxy resin composition for semiconductor encapsulation of the present invention, essential components and, if necessary, other additives are sufficiently uniformly mixed by a mixer or the like, and then further heated. It can be obtained by melt-kneading with a roll or a kneader and the like, or by pulverizing after injection or cooling.
[0048]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[Synthesis Example 1]
Synthesis of hydrocarbon / phenolic resin (P-1)
2000 g of phenol and 400 g of toluene were charged into a reactor having a capacity of 5 liters equipped with a reflux condenser and a Liebig condenser and heated to 170 ° C. to distill 350 g of toluene, so that the water content in the reaction system was 70 ppm. . Next, after cooling the reaction system to 70 ° C. and adding 10 g of boron trifluoride / phenol complex, 400 g of dicyclopentadiene having a water content of 20 ppm was added over 1.5 hours while controlling the reaction temperature at 70 ° C. After the dropwise addition, the reaction was carried out at 100 ° C. for 5 hours. After completion of the reaction, Mg _0.7 Al _0.3 (OH) ₂ (CO _Three ) _0.15 ・ MH ₂ 30 g of hydrotalcite compound represented by O (0.46 ≦ m ≦ 0.54) (synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd., trade name “KW-1000”) was added and stirred for 30 minutes. After deactivating the catalyst, the reaction solution was filtered using filter paper spread with celite. The obtained reaction solution was distilled under reduced pressure at 210 ° C. to obtain 880 g of phenol resin. The amount of phenol remaining in this resin was measured and found to be 10 ppm.
[0049]
The obtained phenol resin (P-1) had a softening point of 96 ° C., a Gardner hue of 13, a residual boron of 5 ppm, and a fluorine content of 1 ppm or less.
Carbon and hydrogen contents by the hydrocarbon analysis method were 83.0% and 7.6%, respectively, and oxygen content by the oxygen determination method was 9.5%.
When the FD mass spectrum of the obtained resin was measured, peaks having molecular weights of 320, 546, 771, 997, and 1223 were detected, and it was confirmed that the resin was composed of molecules having the structure shown in Formula (10).
When the content of the phenolic hydroxyl group was acetylated with acetic anhydride and then determined by back titration, the phenolic hydroxyl group equivalent was 170 g / eq.
[0050]
¹ In the H-NMR analysis, protons bonded to the aromatic ring at δ 6.5 to 7.5 ppm and protons derived from the aliphatic hydrocarbon ring at δ 0.8 to 4.0 ppm are observed in multiple lines, respectively. Absorption of protons due to the carbon-carbon double bond was not observed. Further, the content of phenolic hydroxyl group was determined from the peak area ratio of δ 6.5-8 ppm and δ 0.8-2.5 ppm, and the phenolic hydroxyl group equivalent was 170 g / eq similarly to the result by titration. .
[0051]
Also, ¹³ In the C-NMR analysis, since no signal of 158 ppm of carbon generated when phenol was ether-added to a double bond, it was found that all of the phenol was added by alkylation.
[0052]
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[0053]
Hydrogenation of hydrocarbon alcohol (A-1)
Hydrogenation of said hydrocarbon * phenol resin (P-1) was performed with the following method.
A 1-liter autoclave made of SUS304 equipped with a stirrer was charged with 170 g of the phenol resin (P-1) obtained in Example 1, 340 g of isopropanol, and 10.0 g of Raney nickel, and the inside of the autoclave was replaced with hydrogen. The temperature rose.
Subsequently, while maintaining the reaction system temperature at 180 ° C., the hydrogen pressure was 60 kg / cm. ² To 40kg / cm ² When the pressure decreased until the hydrogen absorption disappeared, the absorption was completed after 8 hours.
The autoclave was cooled, the reaction solution was filtered to remove the catalyst and the catalyst residue, and then the residual reaction solution was distilled and concentrated to obtain 167 g.
[0054]
The carbon and hydrogen contents by the fresh hydrogen analysis method were 80.2% and 10.8%, respectively, and the oxygen content by the oxygen determination method was 9.3%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 332, 564, 795, 1027, and 1259 were detected.
When the hydroxyl equivalent of the obtained derivative was measured, it was 179 g / eq.
Also, ¹ In H-NMR analysis, protons derived from the aliphatic hydrocarbon ring were observed at δ 0.8 to 4.0 ppm in a multiple line, but absorption of protons due to carbon-carbon double bonds was not observed, The proton bonded to the aromatic ring of δ 6.5 to 7.5 ppm disappeared, and it was confirmed that the hydrogenation was completed.
In the analysis by IR, P-1 is 3050 cm. ^-1 The peak derived from the aromatic C—H stretching observed in the vicinity has disappeared, and the obtained resin is the target hydrocarbon alcohol derivative (A-1) represented by the pale yellow formula (11). I confirmed that there was.
[0055]
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[0056]
Synthesis of hydrocarbon epoxy resin (E-1)
Glycidylation of said hydrocarbon alcohol (A-1) was performed by the following method.
179 g of hydrocarbon alcohol (A-1) and 700 g of epichlorohydrin were charged in a 2 liter four-necked flask equipped with a stirrer, reflux condenser and thermometer, and then dissolved and stirred to prepare a reaction system with a pressure of 150 mmHg. The temperature was raised to 68 ° C. The system was reacted for 3.5 hours while continuously adding 100 g of a 48 wt% sodium hydroxide aqueous solution. Water produced by the reaction and water of an aqueous sodium hydroxide solution were decomposed by refluxing the water-epichlorohydrin azeotrope and continuously removed out of the reaction system. After completion of the reaction, the reaction system was returned to normal pressure and heated to a temperature of 110 ° C. to completely remove water in the reaction system. Excess epichlorohydrin was distilled off under normal pressure, and further distilled at 140 ° C. under a reduced pressure of 15 mmHg.
[0057]
300 g of methyl isobutyl ketone and 36 g of a 10 wt% aqueous sodium hydroxide solution were added to the resulting mixture of resin and sodium chloride, and the reaction was carried out at a temperature of 85 ° C. for 1.5 hours. After completion of the reaction, 750 g of methyl isobutyl ketone and 300 g of water were added, and the lower layer sodium chloride aqueous solution was separated and removed. Next, 150 g of water was added to the methyl isobutyl ketone liquid layer for washing, neutralized with phosphoric acid, the aqueous layer was separated, and further washed with 800 g of water to separate the aqueous layer.
Next, after the methyl isobutyl ketone liquid layer was distilled under normal pressure, distillation under reduced pressure was performed at 5 mmHg and 140 ° C. to obtain 220 g of a hydrocarbon epoxy resin (E-1) represented by the following formula (12). The epoxy equivalent of this epoxy resin was 250 g / equivalent.
[0058]
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[0059]
[Synthesis Example 2]
Synthesis of phenolic resin (P-2)
Except for using 2300 g of o-cresol instead of phenol, the reaction and purification were conducted in the same manner as in Example 1 to obtain 940 g of a phenol resin (P-2) represented by the following formula (13).
[0060]
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[0061]
The obtained phenol resin (P-2) had a softening point of 89 ° C., a Gardner hue of 11, residual boron of 5 ppm, and fluorine of 1 ppm or less.
Carbon and hydrogen contents by the hydrocarbon analysis method were 83.0% and 8.1%, respectively, and oxygen content by the oxygen determination method was 9.1%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 348, 588, 828, 1068, and 1308 were detected, and it was confirmed that the resin was composed of molecules having the structure shown in Formula (13). The phenolic hydroxyl group equivalent was 180 g / eq.
¹ In the H-NMR analysis, protons bonded to the aromatic ring at δ 6.5 to 7.5 ppm and protons derived from the aliphatic hydrocarbon ring at δ 0.8 to 4.0 ppm were observed in multiple lines, and carbon was observed. -Absorption of protons due to carbon double bonds was not observed. Further, when the content of phenolic hydroxyl group was determined from the peak area ratio of δ 6.5 to 8 ppm and δ 0.8 to 2.5 ppm, the phenolic hydroxyl group equivalent was 180 g / eq similarly to the result by titration. .
[0062]
Synthesis of hydrocarbon alcohol (A-2)
The reaction was carried out in the same manner as in Example 1 except that 180 g of the hydrocarbon / phenol resin (P-2) was used. As a result, the intended pale yellow hydrocarbon alcohol represented by the following formula (14) ( A-2) 182 g was obtained. When the hydroxyl equivalent of the obtained derivative was measured, it was 187 g / eq.
[0063]
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[0064]
The carbon and hydrogen contents by the fresh hydrogen analysis method were 80.4% and 11.0%, respectively, and the oxygen content by the oxygen determination method was 8.6%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 360, 606, 852, 1098, and 1344 were detected.
When the hydroxyl equivalent of the obtained derivative was measured, it was 186 g / eq.
Also, ¹ In H-NMR analysis, protons derived from the aliphatic hydrocarbon ring were observed at δ 0.8 to 4.0 ppm in a multiple line, but absorption of protons due to carbon-carbon double bonds was not observed, The proton bonded to the aromatic ring of δ 6.5 to 7.5 ppm disappeared, and it was confirmed that the hydrogenation was completed.
In the analysis by IR, (P-1) is 3050 cm. ^-1 The peak derived from the aromatic C—H stretching observed in the vicinity disappeared, and it was confirmed that the obtained resin was the intended pale yellow hydrocarbon alcohol derivative (A-2).
[0065]
Synthesis of hydrocarbon epoxy resin (E-2)
Glycidylation of said hydrocarbon alcohol (A-2) was performed by the following method.
186 g of hydrocarbon alcohol (A-2) and 700 g of epichlorohydrin were charged into a 2 liter four-necked flask equipped with a stirrer, reflux condenser and thermometer, and then dissolved and stirred to prepare a reaction system with a pressure of 150 mmHg. The temperature was raised to 68 ° C. The system was reacted for 3.5 hours while continuously adding 100 g of a 48 wt% sodium hydroxide aqueous solution. Water produced by the reaction and water of an aqueous sodium hydroxide solution were decomposed by refluxing the water-epichlorohydrin azeotrope and continuously removed out of the reaction system. After completion of the reaction, the reaction system was returned to normal pressure and heated to a temperature of 110 ° C. to completely remove water in the reaction system. Excess epichlorohydrin was distilled off under normal pressure, and further distilled at 140 ° C. under a reduced pressure of 15 mmHg.
[0066]
300 g of methyl isobutyl ketone and 36 g of a 10 wt% aqueous sodium hydroxide solution were added to the resulting mixture of resin and sodium chloride, and the reaction was carried out at a temperature of 85 ° C. for 1.5 hours. After completion of the reaction, 750 g of methyl isobutyl ketone and 300 g of water were added, and the lower layer sodium chloride aqueous solution was separated and removed. Next, 150 g of water was added to the methyl isobutyl ketone liquid layer for washing, neutralized with phosphoric acid, the aqueous layer was separated, and further washed with 800 g of water to separate the aqueous layer. Next, after the methyl isobutyl ketone liquid layer was distilled under normal pressure, distillation under reduced pressure was performed at 5 mmHg and 140 ° C. to obtain 210 g of a hydrocarbon epoxy resin (E-2) represented by the following formula (15). The epoxy equivalent of this epoxy resin was 275 g / equivalent.
[0067]
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[0068]
[Synthesis Example 3]
Synthesis of hydrocarbon / phenolic resin (P-3)
Except for using 370 g of tetrahydroindene instead of dicyclopentadiene, the reaction and purification were carried out in the same manner as in Example 1 to obtain 550 g of a phenol resin (P-3) represented by the following formula (16).
[0069]
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[0070]
The obtained phenol resin (P-3) had a softening point of 93 ° C., a Gardner hue of 12, residual boron of 5 ppm, and fluorine of 3 ppm or less. The phenolic hydroxyl group equivalent was 183 g / eq.
The carbon and hydrogen contents by the hydrocarbon analysis method were 82.2% and 7.9%, respectively, and the oxygen content by the oxygen determination method was 9.9%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 308, 522, 734, and 949 were detected, and it was confirmed that the resin was composed of molecules having the structure shown in Formula (16).
When the content of the phenolic hydroxyl group was acetylated with acetic anhydride and then determined by back titration, the phenolic hydroxyl group equivalent was 170 g / eq.
¹ In the H-NMR analysis, protons bonded to the aromatic ring at δ 6.5 to 7.5 ppm and protons derived from the aliphatic hydrocarbon ring at δ 0.8 to 4.0 ppm are observed in multiple lines, respectively. Absorption of protons due to the carbon-carbon double bond was not observed. Further, the content of phenolic hydroxyl group was determined from the peak area ratio of δ 6.5-8 ppm and δ 0.8-2.5 ppm, and the phenolic hydroxyl group equivalent was 183 g / eq similarly to the result by titration. .
Also, ¹³ In C-NMR analysis, a signal of 158 ppm of carbon generated when phenol was ether-added to a double bond was observed, and the etherification ratio was 10%.
[0071]
Synthesis of hydrocarbon alcohol (A-3)
The reaction was carried out in the same manner as in Example 1 except that 183 g of phenol resin (P-3), 400 g of isopropanol, and 10.0 g of Raney nickel were charged, and the intended pale yellow hydrocarbon alcohol represented by the following formula (17) ( A-3) 189 g was obtained.
[0072]
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[0073]
The carbon and hydrogen contents by the fresh hydrogen analysis method were 79.3% and 11.2%, respectively, and the oxygen content by the oxygen determination method was 9.6%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 320, 540, 760, and 980 were detected.
When the hydroxyl equivalent of the obtained derivative was measured, it was 188 g / eq.
Also, ¹ In H-NMR analysis, protons derived from the aliphatic hydrocarbon ring were observed at δ 0.8 to 4.0 ppm in a multiple line, but absorption of protons due to carbon-carbon double bonds was not observed, The proton bonded to the aromatic ring of δ 6.5 to 7.5 ppm disappeared, and it was confirmed that the hydrogenation was completed.
¹³ In the C-NMR analysis, a signal of 68 ppm of carbon generated when ether was added to a cyclic aliphatic hydrocarbon was observed, and the etherification ratio was 10%.
In the analysis by IR, P-1 is 3050 cm. ^-1 The peak derived from the aromatic C—H stretching observed in the vicinity disappeared, and it was confirmed that the obtained resin was the intended pale yellow hydrocarbon alcohol derivative (A-3).
¹³ In C-NMR analysis, a signal of 158 ppm of carbon generated when phenol was ether-added to a double bond was observed, and the etherification ratio was 10%.
[0074]
Synthesis of hydrocarbon epoxy resin (E-3)
Glycidylation of said hydrocarbon alcohol (A-3) was performed by the following method.
Into a 2 liter four-necked flask equipped with a stirrer, reflux condenser and thermometer, 188 g of hydrocarbon alcohol (A-3) and 700 g of epichlorohydrin were charged, and after the reaction in the same manner as in Example 1, a post-treatment was performed. 260 g of a hydrocarbon epoxy resin (E-3) represented by the following formula (18) was obtained. The epoxy equivalent of this epoxy resin was 270 g / equivalent.
[0075]
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[0076]
[Synthesis Example 4]
Synthesis of hydrocarbon / phenolic resin (P-4)
2000 g of phenol and 400 g of toluene were charged into a reactor having a capacity of 5 liters equipped with a reflux condenser and a Liebig condenser and heated to 170 ° C. to distill 350 g of toluene, so that the water content in the reaction system was 70 ppm. . Next, the reaction system was cooled to 70 ° C., 10 g of boron trifluoride / phenol complex was added, and 360 g of isoprene having a water content of 20 ppm was gradually added over 1.5 hours while controlling the reaction temperature at 70 ° C. The reaction was conducted at 100 ° C. for 5 hours. After completion of the reaction, Mg _0.7 Al _0.3 (OH) ₂ (CO _Three ) _0.15 ・ MH ₂ 15 g of hydrotalcite compound represented by O (0.46 ≦ m ≦ 0.54) (synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd., trade name “KW-1000”) was added and stirred for 30 minutes. After deactivating the catalyst, the reaction solution was filtered using filter paper spread with celite. The obtained reaction solution was subjected to thin film distillation at 200 ° C. to obtain 400 g of a liquid phenol resin as a distillation fraction. The amount of phenol remaining in this resin was measured and found to be 10 ppm.
[0077]
The obtained phenol resin (P-4) had residual boron of 5 ppm and fluorine of 3 ppm or less. The melt viscosity at 150 ° C. was 0.15 poise. The phenolic hydroxyl group equivalent was 155.
Carbon and hydrogen contents by the hydrocarbon analysis method were 80.7% and 8.9%, respectively, and oxygen content by the oxygen determination method was 10.5%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 256 and 326 were detected, and it was confirmed that the resin was composed of molecules having the structure shown in the following formula (19).
[0078]
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[0079]
When the content of the phenolic hydroxyl group was acetylated with acetic anhydride and then obtained by back titration, the phenolic hydroxyl group equivalent was 155 g / eq.
¹ In the H-NMR analysis, protons bonded to the aromatic ring at δ 6.5 to 7.5 ppm and protons derived from the aliphatic hydrocarbon ring at δ 0.8 to 4.0 ppm are observed in multiple lines, respectively. Absorption of protons due to the carbon-carbon double bond was not observed. Further, the phenolic hydroxyl group content was determined from the peak area ratio of δ 6.5-8 ppm and δ 0.8-2.5 ppm, and the phenolic hydroxyl group equivalent was 155 g / eq similarly to the result by titration. .
Also, ¹³ In the C-NMR analysis, since no signal of 158 ppm of carbon generated when phenol was ether-added to a double bond, it was found that all of the phenol was added by alkylation.
[0080]
Synthesis of hydrocarbon alcohol (A-4)
A reaction was carried out in the same manner as in Example 1 except that 155 g of the above phenol resin (P-4) was used, to obtain 159 g of the intended pale yellow hydrocarbon alcohol (A-4).
[0081]
The carbon and hydrogen contents by the fresh hydrogen analysis method were 77.7% and 12.3%, respectively, and the oxygen content by the oxygen determination method was 10.1%.
When the FD mass spectrum of the obtained resin was measured, peaks with molecular weights of 268 and 338 were detected.
When the hydroxyl equivalent of the obtained derivative was measured, it was 161 g / eq.
Also, ¹ In H-NMR analysis, protons derived from the aliphatic hydrocarbon ring were observed at δ 0.8 to 4.0 ppm in a multiple line, but absorption of protons due to carbon-carbon double bonds was not observed, The proton bonded to the aromatic ring of δ 6.5 to 7.5 ppm disappeared, and it was confirmed that the hydrogenation was completed.
In the analysis by IR, P-1 is 3050 cm. ^-1 The peak derived from the aromatic C—H stretching observed in the vicinity has disappeared, and the obtained resin is an intended pale yellow hydrocarbon alcohol derivative (A-4) represented by the following formula (20): It was confirmed that.
[0082]
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[0083]
Synthesis of hydrocarbon epoxy resin (E-4)
Glycidylation of said hydrocarbon alcohol (A-4) was performed by the following method.
Into a 2 liter four-necked flask equipped with a stirrer, reflux condenser and thermometer, 161 g of hydrocarbon alcohol (A-4) and 700 g of epichlorohydrin were charged, and after the reaction in the same manner as in Example 1, a post-treatment was performed. 220 g of hydrocarbon epoxy resin (E-4) represented by the following formula (21) was obtained. The epoxy equivalent of this epoxy resin was 245 g / equivalent.
[0084]
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[0085]
[Synthesis Example 5]
Synthesis of hydrocarbon / phenolic resin (P-5)
2000 g of phenol and 400 g of toluene were charged into a reactor having a capacity of 5 liters equipped with a reflux condenser and a Liebig condenser and heated to 170 ° C. to distill 350 g of toluene, so that the water content in the reaction system was 70 ppm. . Next, the reaction system was cooled to 70 ° C., 10 g of boron trifluoride / phenol complex was added, and 410 g of limonene having a water content of 20 ppm was gradually added over 1.5 hours while controlling the reaction temperature at 70 ° C. The reaction was conducted at 100 ° C. for 5 hours. After completion of the reaction, Mg _0.7 Al _0.3 (OH) ₂ (CO _Three ) _0.15 ・ MH ₂ 15 g of hydrotalcite compound represented by O (0.46 ≦ m ≦ 0.54) (synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd., trade name “KW-1000”) was added and stirred for 30 minutes. After deactivating the catalyst, the reaction solution was filtered using filter paper spread with celite. The obtained reaction solution was subjected to thin film distillation at 200 ° C. to obtain 570 g of a phenol resin (P-5) as a distillation fraction. The amount of phenol remaining in this resin was measured and found to be 10 ppm.
[0086]
The obtained phenol resin (P-5) had a softening point of 93 ° C., a Gardner hue of 12, residual boron of 5 ppm, and fluorine of 3 ppm or less.
Carbon and hydrogen contents by the hydrocarbon analysis method were 81.5% and 8.6%, respectively, and oxygen content by the oxygen determination method was 10.0%.
When the FD mass spectrum of the obtained resin was measured, a peak with a molecular weight of 324 was detected, and it was confirmed that the resin was composed of molecules (n = 0) having the structure shown in the following formula (22).
[0087]
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[0088]
When the content of the phenolic hydroxyl group was acetylated with acetic anhydride and then obtained by back titration, the phenolic hydroxyl group equivalent was 161 g / eq.
¹ In the H-NMR analysis, protons bonded to the aromatic ring at δ 6.5 to 7.5 ppm and protons derived from the aliphatic hydrocarbon ring at δ 0.8 to 4.0 ppm are observed in multiple lines, respectively. Absorption of protons due to the carbon-carbon double bond was not observed. Further, when the content of phenolic hydroxyl group was determined from the peak area ratio of δ 6.5 to 8 ppm and δ 0.8 to 2.5 ppm, the phenolic hydroxyl group equivalent was 161 g / eq similarly to the result by titration. .
Also, ¹³ In the C-NMR analysis, since no signal of 158 ppm of carbon generated when phenol was ether-added to a double bond, it was found that all of the phenol was added by alkylation.
[0089]
Synthesis of hydrocarbon alcohol (A-5)
The reaction was carried out in the same manner as in Example 1 except that 161 g of the above phenol resin (P-5) was used. As a result, the intended pale yellow hydrocarbon alcohol (A- 5) 163 g was obtained.
[0090]
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[0091]
Also, ¹ In the H-NMR analysis, the proton bonded to the aromatic ring at δ 6.5 to 7.5 ppm disappeared, and it was confirmed that the hydrogenation was completed.
Carbon and hydrogen contents by the fresh hydrogen analysis method were 78.6% and 11.9%, respectively, and oxygen content by the oxygen determination method was 9.6%.
When the FD mass spectrum of the obtained resin was measured, a peak with a molecular weight of 336 was detected.
When the hydroxyl equivalent of the obtained derivative was measured, it was 168 g / eq.
Also, ¹ In H-NMR analysis, protons derived from the aliphatic hydrocarbon ring were observed at δ 0.8 to 4.0 ppm in a multiple line, but absorption of protons due to carbon-carbon double bonds was not observed, The proton bonded to the aromatic ring of δ 6.5 to 7.5 ppm disappeared, and it was confirmed that the hydrogenation was completed.
In the analysis by IR, P-1 is 3050 cm. ^-1 The peak derived from the aromatic C—H stretching observed in the vicinity disappeared, and it was confirmed that the obtained resin was the intended pale yellow hydrocarbon alcohol derivative (A-1).
[0092]
Synthesis of hydrocarbon epoxy resin (E-5)
Glycidylation of said hydrocarbon alcohol (A-5) was performed by the following method. Into a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 168 g of hydrocarbon alcohol (A-5) and 700 g of epichlorohydrin were charged, and after the reaction in the same manner as in Example 1, a post-treatment was performed. 210 g of hydrocarbon epoxy resin (E-5) represented by the following formula (24) was obtained. The epoxy equivalent of this epoxy resin was 250 g / equivalent.
[0093]
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[0094]
Example 1
70 g of epoxy resin (E-1) produced in Synthesis Example 1, 30 g of phenol novolac resin (manufactured by Arakawa Chemical Industries, Ltd., trade name “Tamanol 758”), 0.2 g of triphenylphosphine, fused silica powder (trade name “ A composition comprising 353 g of “Hyuzu Rex RD-8” (manufactured by Tatsumori Co., Ltd.) and the additives shown in Table 1 was prepared, and the composition was melt-kneaded at 85 ° C. for 10 minutes using a kneader. After cooling, the mixture was pulverized to obtain an epoxy resin molding material.
The obtained molding material was tableted, and the tableted molding material was 175 ° C. and 70 kg / cm using a low-pressure transfer molding machine. ² After being sealed under a condition of 120 seconds, it was post-cured at 180 ° C. for 5 hours. The releasability during transfer molding was good. Using the obtained cured product, a 6 × 6 mm chip is sealed in a 52p package for a solder crack test, and a 6 × 6 mm chip is sealed in a 16pSOP package for a solder moisture resistance test. An element was produced. The sealed test element was subjected to the following solder crack test and solder moisture resistance test. The results are shown in Table 1.
[0095]
(Solder crack test): The sealed test element was treated in an environment of 85 ° C. and 85% RH for 48 hours and 72 hours, and then immersed in a solder bath at 280 ° C. for 10 seconds, and then external cracks were observed with a microscope.
(Solder moisture resistance average life (hours)): The sealed test element was treated in an environment of 85 ° C. and 85% RH for 48 hours and 72 hours, and then immersed in a solder bath at 280 ° C. for 10 seconds, followed by a pressure cooker test. (125 ° C., 100% RH) was performed, and the time until a 50% circuit oven failure occurred was measured.
[0096]
(Examples 2 to 5)
Example except that the epoxy resins (E-2), (E-3), (E-4) and (E-5) produced in Synthesis Examples 2 to 5 were used instead of the epoxy resin (E-1). The molding material was obtained in the same manner as in No. 1, and each test was performed. The results are shown in Table 1.
[0097]
(Comparative Example 1)
Example 1 except that the epoxy resin (E-1) was replaced with 68 g of novolak epoxy resin (trade name “Epiclon N-660”, manufactured by Dainippon Ink and Chemicals, Inc.), and the mixing ratio shown in Table 1 was used. A molding material was obtained and tested. The results are shown in Table 1.
[0098]
[Table 1]

[0099]
(Example 6)
The epoxy resin (E-1) produced in Synthesis Example 1 and the commercially available phenol resin shown in Table 2 are mixed with the curing accelerator shown in Table 2 to obtain an epoxy resin composition, and then the solvent shown in Table 2 is added. Then, after preparing an epoxy resin varnish (resin component is 60% by weight), an E glass cloth was immersed in the epoxy resin varnish. This varnish-impregnated cloth was dried in a drying chamber at 160 ° C. for 4 minutes to obtain a B-stage prepreg.
The obtained prepreg was cut into eight prepregs, and further, eight prepregs were stacked, and two electrolytic copper foils having a thickness of 35 μm were stacked on both sides to obtain 40 kg / cm. ² While being pressurized, the laminate was heated at 175 ° C. for 120 minutes to obtain a laminate. Table 2 shows the physical properties of the obtained cured laminate.
[0100]
(Examples 7 to 10)
Implemented except that the phenol resins (E-2), (E-3), (E-4) and (E-5) produced in Examples 2 to 5 were used instead of the epoxy resin (E-1). A laminate was prepared in the same manner as in Example 6. The test results are shown in Table 2.
[0101]
(Comparative Example 2)
The epoxy resin (E-1) was replaced with 68 g of novolak epoxy resin (trade name “Epiclon N-660”, manufactured by Dainippon Ink and Chemicals, Inc.), and the mixture ratio shown in Table 2 was used. Thus, a laminated board was prepared. The test results are shown in Table 2.
[0102]
[Table 2]

[0103]
【The invention's effect】
The hydrocarbon alcohol of the present invention is a saturated hydrocarbon alcohol having an alicyclic structure in which a hydrocarbon group is a nodule and the aromatic ring is hydrogenated. When the nodule is a chain hydrocarbon group, solubility, reaction It is ideal as a raw material for epoxy resins, polyester resins, polycarbonate resins, and polyurethane resins, which are excellent in heat resistance and heat stability, and have excellent flexibility, heat resistance, and weather resistance. On the other hand, when the nodule group is a rigid and bulky cyclic hydrocarbon group, it is optimal as a raw material for each of the above resins excellent in moisture resistance, heat resistance and electrical characteristics. These resins are also useful as raw materials for various industrial products including photosensitive agents and as additives for various polymer materials.
[0104]
The composition using the epoxy resin of the present invention has preferable characteristics as an epoxy resin composition for a semiconductor encapsulant, a laminate, and a solder resist.
For example, when used as a semiconductor encapsulant, the resulting cured product has very good moisture resistance, and has a high glass transition point and thus has excellent heat resistance. Therefore, the cured product is excellent in heat resistance, and even if the semiconductor package is subjected to a sudden temperature change during soldering of the lead wire, a crack occurs in the resin molded part, or the interface between the lead wire and the resin is It does not deteriorate at all, and is excellent in mechanical properties and electrical characteristics.
[0105]
In addition, since the composition using the epoxy resin of the present invention is excellent in heat resistance, adhesiveness, moisture resistance, etc., when used as an epoxy resin composition for a laminated board, it can be heated by far infrared rays, infrared rays, soldering, etc. The resulting measling phenomenon and phase separation do not occur, and warpage is extremely small, dimensional stability and through hole adhesion reliability are excellent, and drilling workability can also be improved. Furthermore, when the composition using the epoxy resin of this invention is used, it has the characteristics that the laminated board excellent in the electrical property can be manufactured. That is, in order to manufacture printed circuit boards for high-speed electronic devices and high-frequency devices, it is essential to improve the dielectric properties, and it is known that the dielectric properties depend on the structure of the epoxy resin used. The laminate using the epoxy resin composition according to the present invention has very excellent dielectric properties.
[0106]
When the composition using the epoxy resin of the present invention is used for a solder resist, adhesion, electrical insulation and electric resistance, solder heat resistance, non-whitening property to water-soluble flux for levelers, excellent resistance to solvents such as methylene chloride Excellent in acid and alkali resistance, plating resistance, PCT resistance and the like.
[0107]
By the production method of the present invention, the hydrocarbon alcohol and the hydrocarbon epoxy resin can be easily produced.

Claims (8)

General formula (1)
[Chemical 1]
hc- (R1 -hc) n-R1 -hc
(In the formula, hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups are directly bonded to the saturated cyclic hydrocarbon group. R1 represents the number of carbon atoms. (It is a saturated hydrocarbon group of 4 to 25. Note that two hc linked to R1 are not bonded to the same carbon in R1. N is 0 or an integer of 1 to 30.)
Hydrocarbon alcohol represented by General formula (2)
[Chemical 2]
hc- (R2 -hc) n-R2 -hc
(In the formula, hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups in hc are directly bonded to the cyclic saturated hydrocarbon group. R2 has 5 carbon atoms. A saturated polycyclic hydrocarbon group of ˜25, wherein the two hc linked to R2 are not bonded to the same carbon in R2.n is 0 or an integer of 1-30.)
Hydrocarbon alcohol represented by General formula (3)
[Chemical 3]
hp- (R1 -hp) n-R1 -hp
(In the formula, hp represents a polyhydroxyphenyl group having 6 to 16 carbon atoms. The hydroxyl group in hp is a phenolic hydroxyl group, and 1 to 3 are bonded to hp. The phenolic hydroxyl group is 1 to 3 in number. R1 is a hydrocarbon group having 4 to 25 carbon atoms, wherein two hps linked to R1 are not bonded to the same carbon in R1, and n is an integer of 0 or 1-30. )
The hydrocarbon-phenol resin represented by these is hydrogenated in presence of a metal catalyst, The manufacturing method of the hydrocarbon alcohol of Claim 1 characterized by the above-mentioned. General formula (4)
[Formula 4]
hp- (R2-hp) n-R2-hp
(In the formula, hp represents a polyhydroxyphenyl group having 6 to 16 carbon atoms. The number of phenolic hydroxyl groups in hp is 1 to 3. R2 is a polycyclic hydrocarbon group having 5 to 25 carbon atoms. Note that two hps connected to R2 are not bonded to the same carbon in R2, and n is 0 or an integer of 1 to 30.)
The method for producing a hydrocarbon alcohol according to claim 2, wherein the hydrocarbon / phenol resin represented by the formula (2) is hydrogenated in the presence of a metal catalyst. General formula (5)
[Chemical formula 5]
gc- (R1 -gc) n-R1 -gc
(In the formula, gc represents an X—O— group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. X represents a glycidyl group, and the number of X—O— groups in gc is 1 to 3. Directly bonded to a saturated cyclic hydrocarbon group, R1 is a saturated hydrocarbon group having 4 to 25 carbon atoms, and two gc linked to R1 are not bonded to the same carbon in R1. 0 or an integer of 1 to 30). General formula (6)
[Chemical 6]
gc- (R2 -gc) n-R2 -gc
(In the formula, gc represents an X—O— group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. X represents a glycidyl group, and the number of X—O— groups in gc is 1 to 3. Directly bonded to a saturated cyclic hydrocarbon group R2 is a saturated polycyclic hydrocarbon group having 5 to 25 carbon atoms, and two gc linked to R2 are not bonded to the same carbon in R2. N is 0 or an integer from 1 to 30.)
Hydrocarbon epoxy resin represented by General formula (1)
[Chemical 7]
hc- (R1 -hc) n-R1 -hc
(In the formula, hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups are directly bonded to the saturated cyclic hydrocarbon group. R1 represents the number of carbon atoms. (It is a saturated hydrocarbon group of 4 to 25. Note that two hc linked to R1 are not bonded to the same carbon in R1. N is 0 or an integer of 1 to 30.)
The method for producing a hydrocarbon epoxy resin according to claim 5, wherein the hydrocarbon alcohol represented by the formula (1) is reacted with epihalohydrin in the presence of a base. General formula (2)
[Chemical 8]
hc- (R2-hc) n-R2-hc
(Wherein hc represents a hydroxyl group-containing saturated cyclic hydrocarbon group having 6 to 16 carbon atoms. In addition, 1 to 3 hydroxyl groups in hc are directly bonded to the saturated cyclic hydrocarbon group. R2 has 5 carbon atoms. A saturated polycyclic hydrocarbon group of ˜25, wherein two gc's connected to R2 are not bonded to the same carbon in R2.n is 0 or an integer of 1-30.)
The method for producing a hydrocarbon epoxy resin according to claim 6, wherein the hydrocarbon alcohol represented by the formula (1) is reacted with epihalohydrin in the presence of a base.